2 Thermodynamic Property
Models
This section describes the available thermodynamic property models in the
Aspen Physical Property System. The following table provides a list of
available models, with corresponding Aspen Physical Property System model
names. The table provides phase types for which the model can be used and
information on use of the model for pure components and mixtures.
Aspen Physical Property System thermodynamic property models include
classical thermodynamic property models, such as activity coefficient models
and equations of state, as well as solids and electrolyte models. The models
are grouped according to the type of property they describe.
Thermodynamic Property Models
Phases: V = Vapor; L = Liquid; S = Solid. An X indicates applicable to Pure or
Mixture.
EquationofState Models
Property Model Model Name(s) Phase(s)Pure Mixture
ASME Steam Tables ESH2O0,ESH2O V L X
BWRLeeStarling ESBWR0, ESCSTBWR V L X X
BenedictWebbRubinStarling ESBWRS, ESBWRS0 V L X X
HaydenO'Connell ESHOC0,ESHOC V X X
HF equationofstate ESHF0, ESHF V X X
Ideal Gas ESIG V X X
LeeKesler ESLK V L X
LeeKeslerPlcker ESLKP0,ESLKP V L X X
NBS/NRC Steam Tables ESSTEAM0,ESSTEAM V L X
Nothnagel ESNTH0,ESNTH V X X
PengRobinson ESPR0, ESPR V L X X
Standard PengRobinson ESPRSTD0,ESPRSTD V L X X
PengRobinsonWongSandler ESPRWS0,ESPRWS V L X X
PengRobinsonMHV2 ESPRV20,ESPRV2 V L X X
Predictive SRK ESRKSV10, ESRKSV1 V L X X
2 Thermodynamic Property Models 13
Property Model Model Name(s) Phase(s)Pure Mixture
RedlichKwong ESRK0, ESRK V X X
RedlichKwongAspen ESRKA0,ESRKA V L X X
Standard RedlichKwongSoave ESRKSTD0,ESRKSTD V L X X
RedlichKwongSoaveBoston
Mathias
ESRKS0,ESRKS V L X X
RedlichKwongSoaveWong
Sandler
ESRKSWS0, ESRKSWSV L X X
RedlichKwongSoaveMHV2 ESRKSV20, ESRKSV2 V L X X
SchwartzentruberRenon ESRKU0,ESRKU V L X X
SoaveRedlichKwong ESSRK, ESSRK0 V L X X
VPA/IKCAPE equationofstate ESVPA0, ESVPA V X X
PengRobinson Alpha functions V L X
RKSoave Alpha functions V L X
HuronVidal mixing rules V L X
MHV2 mixing rules V L X
PSRK mixing rules V L X
WongSandler mixing rules V L X
Activity Coefficient Models (Including Electrolyte Models)
Property Model Model Name Phase(s)Pure Mixture
BromleyPitzer(ChienNull) GMPT2 L X
ChienNull GMCHNULL L X
Constant Activity Coefficient GMCONS S X
Electrolyte NRTL GMELC L L1 L2 X
Ideal Liquid GMIDL L X
NRTL(NonRandomTwoLiquid) GMRENON L L1 L2 X
Pitzer GMPT1 L X
Polynomial Activity Coefficient GMPOLY L S X
RedlichKister GMREDKIS L S X
ScatchardHildebrand GMXSH L X
ThreeSuffix Margules GMMARGUL L S X
UNIFAC GMUFAC L L1 L2 X
UNIFAC (Lyngby modified) GMUFLBY L L1 L2 X
UNIFAC (Dortmund modified) GMUFDMD L L1 L2 X
UNIQUAC GMUQUAC L L1 L2 X
van Laar GMVLAAR L X
Wagner interaction parameter GMWIP S X
Wilson GMWILSON L X
Wilson model with liquid molar
volume
GMWSNVOL L X
Vapor Pressure and Liquid Fugacity Models
Property Model Model Name Phase(s)Pure Mixture
Extended Antoine/Wagner PL0XANT L L1 L2 X
14 2 Thermodynamic Property Models
Property Model Model Name Phase(s)Pure Mixture
ChaoSeader PHL0CS L X
GraysonStreed PHL0GS L X
KentEisenberg ESAMIN L X
MaxwellBonnell PL0MXBN L L1 L2 X
Solid Antoine PS0ANT S X
Heat of Vaporization Models
Property Model Model Name Phase(s)Pure Mixture
Watson / DIPPR / IKCAPE DHVLWTSN L X
ClausiusClapeyron Equation DHVLWTSN L X
Molar Volume and Density Models
Property Model Model Name Phase(s)Pure Mixture
API Liquid Volume VL2API L X
BrelviO'Connell VL1BROC L X
Clarke Aqueous Electrolyte
Volume
VAQCLK L X
Costald Liquid Volume VL0CTD,VL2CTD L X X
DebyeHckel Volume VAQDH L X
Liquid Constant Molar Volume VL0CONS L X
Rackett / DIPPR / IKCAPE
Liquid Volume
VL0RKT,VL2RKT L X
Rackett Mixture Liquid Volume VL2RKT L X X
Modified Rackett VL2MRK L X X
Aspen/DIPPR/IKCAPE Solid
Molar Volume
VS0POLY S X
Liquid Volume Quadratic Mixing
Rule
VL2QUAD L X
Heat Capacity Models
Property Model Model Name Phase(s)Pure Mixture
Aqueous Infinite Dilution Heat
Capacity Polynomial
L X
CrissCobble Aqueous Infinite
Dilution Ionic Heat Capacity
L X
DIPPR / IKCAPE Liquid Heat
Capacity
HL0DIP L X
Ideal Gas Heat Capacity / DIPPR V X X
Solids Heat Capacity Polynomial HS0POLY S X
Solubility Correlation Models
Property Model Model Name Phase(s)Pure Mixture
Henry's constant HENRY1 L X
Water solubility L X
2 Thermodynamic Property Models 15
Other Models
Property Model Model Name Phase(s)Pure Mixture
Cavett Liquid Enthalpy
Departure
DHL0CVT, DHL2CVT L X X
BARIN Equations for Gibbs
Energy, Enthalpy, Entropy and
Heat Capacity
S L V X
Electrolyte NRTL Enthalpy HAQELC, HMXELC L X
Electrolyte NRTL Gibbs Energy GAQELC, GMXELC L X
Liquid Enthalpy from Liquid Heat
Capacity Correlation
DHL0DIP L X X
Enthalpies Based on Different
Reference States
DHL0HREF L V X X
EquationofState Models
The Aspen Physical Property System has 20 builtin equationofstate
property models. This section describes the equationofstate property models
available.
Model Type
ASME Steam Tables Fundamental
BWRLeeStarling Virial
BenedictWebbRubinStarling Virial
HaydenO'Connell Virial and association
HF EquationofState Ideal and association
HuronVidal mixing rules Mixing rules
Ideal Gas Ideal
LeeKesler Virial
LeeKeslerPlcker Virial
MHV2 mixing rules Mixing rules
NBS/NRC Steam Tables Fundamental
Nothnagel Ideal
PengRobinson Cubic
Standard PengRobinson Cubic
PengRobinson Alpha functions Alpha functions
PengRobinsonMHV2 Cubic
PengRobinsonWongSandler Cubic
Predictive SRK Cubic
PSRK mixing rules Mixing rules
RedlichKwong Cubic
RedlichKwongAspen Cubic
Standard RedlichKwongSoave Cubic
RedlichKwongSoaveBostonMathias Cubic
RedlichKwongSoaveMHV2 Cubic
16 2 Thermodynamic Property Models
Model Type
RedlichKwongSoaveWongSandler Cubic
RKSoave Alpha functions Alpha functions
SchwartzentruberRenon Cubic
SoaveRedlichKwong Cubic
SRKKabadiDanner Cubic
SRKML Cubic
VPA/IKCAPE equationofstate Ideal and association
WongSandler mixing rules Mixing rules
ASME Steam Tables
The ASME steam tables are implemented like any other equationofstate in
the Aspen Physical Property System. The steam tables can calculate any
thermodynamic property of water or steam and form the basis of the STEAM
TA property method. There are no parameter requirements. The ASME steam
tables are less accurate than the NBS/NRC steam tables.
References
ASME Steam Tables, Thermodynamic and Transport Properties of Steam,
(1967).
K. V. Moore, Aerojet Nuclear Company, prepared for the U.S. Atomic Energy
Commision, ASTEM  A Collection of FORTRAN Subroutines to Evaluate the
1967 ASME equations of state for water/steam and derivatives of these
equations.
BWRLeeStarling
The BenedictWebbRubinLeeStarling equationofstate is the basis of the
BWRLS property method. It is a generalization by Lee and Starling of the
virial equationofstate for pure fluids by Benedict, Webb and Rubin. The
equation is used for nonpolar components, and can manage hydrogen
containing systems.
General Form:
Where:
Mixing Rules:
2 Thermodynamic Property Models 17
Where:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCBWR T
ci
TC X 5.0 2000.0 TEMPERATURE
VCBWR V
ci
*
VC X 0.001 3.5 MOLE
VOLUME
BWRGMA
i
OMEGA X 0.5 3.0
BWRKV
c
ij
0 X 5.0 1.0
BWRKT
q
ij
0 X 5.0 1.0
Binary interaction parameters BWRKV and BWRKT are available in the Aspen
Physical Property System for a large number of components. (See Physical
Property Data, Chapter 1).
References
M.R. Brul, C.T. Lin, L.L. Lee, and K.E. Starling, AIChE J., Vol. 28, (1982) p.
616.
Brul et al., Chem. Eng., (Nov., 1979) p. 155.
Watanasiri et al., AIChE J., Vol. 28, (1982) p. 626.
BenedictWebbRubinStarling
The BenedictWebbRubinStarling equationofstate is the basis of the BWRS
property method. It is a modification by Han and Starling of the virial
equationofstate for pure fluids by Benedict, Webb and Rubin. This equation
ofstate can be used for hydrocarbon systems that include the common light
gases, such as H
2
S, CO
2
and N
2
.
The form of the equationofstate is:
Where:
18 2 Thermodynamic Property Models
k
ij
= k
ji
In the mixing rules given above, A
0i
, B
0i
, C
0i
, D
0i
, E
0i
, a
i
, b
i
, c
i
, d
i
, o
i
,
i
are pure
component constants which can be input by the user. If the values of these
parameters are not given, the Aspen Physical Property System will calculate
them using the critical temperature, the critical volume (or critical density),
the acentric factor and generalized correlations given by Han and Starling.
When water is present, by default BenedictWebbRubinStarling uses the
steam table to calculate the enthalpy, entropy, Gibbs energy, and molar
volume of water. The total properties are molefraction averages of these
values with the properties calculated by the equation of state for other
2 Thermodynamic Property Models 19
components. Fugacity coefficient is not affected. An option code can disable
this use of the steam table.
For best results, the binary parameter k
ij
must be regressed using phase
equilibrium data such as VLE data.
Parameter
Name/
Element
SymbolDefault MDS Lower
Limit
Upper
Limit
Units
BWRSTC T
ci
TC x 5.0 2000.0TEMPERATURE
BWRSVC V
ci
VC x 0.001 3.5 MOLEVOLUME
BWRSOM e
i
OMEGA x 0.5 2.0
BWRSA/1 B
0i
fcn(e
i
,V
ci
, T
ci
) x MOLEVOLUME
BWRSA/2 A
0i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE * MOLE
VOL^2
BWRSA/3 C
0i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE *
TEMPERATURE^2 *
MOLEVOLUME^2
BWRSA/4
i
fcn(e
i
,V
ci
, T
ci
) x MOLEVOLUME^2
BWRSA/5 b
i
fcn(e
i
,V
ci
, T
ci
) x MOLEVOLUME^2
BWRSA/6 a
i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE * MOLE
VOL^3
BWRSA/7 o
i
fcn(e
i
,V
ci
, T
ci
) x MOLEVOLUME^3
BWRSA/8 c
i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE *
TEMPERATURE^2 *
MOLEVOLUME^3
BWRSA/9 D
0i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE *
TEMPERATURE^3 *
MOLEVOLUME^2
BWRSA/10 d
i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE *
TEMPERATURE * MOLE
VOLUME^3
BWRSA/11 E
0i
fcn(e
i
,V
ci
, T
ci
) x PRESSURE *
TEMPERATURE^4 *
MOLEVOLUME^2
BWRAIJ k
ij
x
Constants Used with the correlations of Han and Starling
Parameter Methane Ethane Propane nButane
B
0i
0.723251 0.826059 0.964762 1.56588
A
0i
7520.29 13439.30 18634.70 32544.70
C
0i
2.71092x10
8
2.95195x10
9
7.96178x10
9
1.37436x10
10
D
0i
1.07737x10
10
2.57477x10
11
4.53708x10
11
3.33159x10
11
E
0i
3.01122x10
10
1.46819x10
13
2.56053x10
13
2.30902x10
12
b
i
0.925404 3.112060 5.462480 9.140660
a
i
2574.89 22404.50 40066.40 71181.80
d
i
47489.1 702189.0 1.50520x10
7
3.64238x10
7
o
i
0.468828 0.909681 2.014020 4.009850
c
i
4.37222x10
8
6.81826x10
9
2.74461x10
10
7.00044x10
10
20 2 Thermodynamic Property Models
Parameter Methane Ethane Propane nButane
i
1.48640 2.99656 4.56182 7.54122
Parameter nPentane nHexane nHeptane nOctane
B
0i
2.44417 2.66233 3.60493 4.86965
A
0i
51108.20 45333.10 77826.90 81690.60
C
0i
2.23931x10
10
5.26067x10
10
6.15662x10
10
9.96546x10
10
D
0i
1.01769x10
12
5.52158x10
12
7.77123x10
12
7.90575x10
12
E
0i
3.90860x10
13
6.26433x10
14
6.36251x10
12
3.46419x10
13
b
i
16.607000 29.498300 27.441500 10.590700
a
i
162185.00 434517.00 359087.00 131646.00
d
i
3.88521x10
7
3.27460x10
7
8351150.0 1.85906x10
8
o
i
7.067020 9.702300 21.878200 34.512400
c
i
1.35286x10
11
3.18412x10
11
3.74876x10
11
6.42053x10
11
i
11.85930 14.87200 24.76040 21.98880
References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
M. S. Han, and K. E. Starling , "Thermo Data Refined for LPG. Part 14:
Mixtures", Hydrocarbon Processing, Vol. 51, No. 5, (1972), p.129.
K. E. Starling, "Fluid Themodynamic Properties for Light Petroleum Systems",
Gulf Publishing Co., Houston, Texas (1973).
HaydenO'Connell
The HaydenO'Connell equationofstate calculates thermodynamic properties
for the vapor phase. It is used in property methods NRTLHOC, UNIFHOC,
UNIQHOC, VANLHOC, and WILSHOC, and is recommended for nonpolar,
polar, and associating compounds. HaydenO'Connell incorporates the
chemical theory of dimerization. This model accounts for strong association
and solvation effects, including those found in systems containing organic
acids, such as acetic acid. The equationofstate is:
Where:
 For nonpolar, nonassociating species:
, with
2 Thermodynamic Property Models 21
, where
 For polar, associating species:
, with
, where
 For chemically bonding species:
, and
CrossInteractions
The previous equations are valid for dimerization and crossdimerization if
these mixing rules are applied:
q = 0 unless a special solvation contribution can be justified (for example, i
and j are in the same class of compounds). Many q values are present in the
Aspen Physical Property System.
Chemical Theory
When a compound with strong association is present in a mixture,
the entire mixture is treated according to the chemical theory of dimerization.
22 2 Thermodynamic Property Models
The chemical reaction for the general case of a mixture of dimerizing
components i and j is:
Where i and j refer to the same component.
The equationofstate becomes:
with
In this case, molar volume is equal to V/n
t
.
This represents true total volume over the true number of species n
t
.
However, the reported molar volume is V/n
a
.
This represents the true total volume over the apparent number of species n
a
.
If dimerization does not occur, n
a
is defined as the number of species. V/n
a
reflects the apparently lower molar volume of an associating gas mixture.
The chemical equilibrium constant for the dimerization reaction on pressure
basis K
p
, is related to the true mole fractions and fugacity coefficients:
Where:
y
i
and y
j
= True mole fractions of monomers
y
ij
= True mole fraction of dimer
i
= True fugacity coefficient of component i
K
ij
= Equilibrium constant for the dimerization of i and j, on a
pressure basis
=
o
ij
= 1 for i=j
=
0 for
Apparent mole fractions y
i
a
are reported, but in the calculation real mole
fractions y
i
, y
j
, and y
ij
are used.
The heat of reaction due to each dimerization is calculated according to:
The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles is added to the molar enthalpy
departure .
Parameter Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
2 Thermodynamic Property Models 23
Parameter Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
RGYR r
i
gyr
10
11
5x10
9
LENGTH
MUP p
i
0.0 5x10
24
DIPOLEMOMENT
HOCETA q 0.0 X
The binary parameters HOCETA for many component pairs are available in the
Aspen Physical Property System. These parameters are retrieved
automatically when you specify any of the following property methods: NRTL
HOC, UNIFHOC, UNIQHOC, VANLHOC, and WILSHOC.
References
J.G. Hayden and J.P. O'Connell, "A Generalized Method for Predicting Second
Virial Coefficients," Ind. Eng. Chem., Process Des. Dev., Vol. 14,No. 3,
(1974), pp. 209 216.
HF EquationofState
HF forms oligomers in the vapor phase. The nonideality in the vapor phase is
found in important deviations from ideality in all thermodynamic properties.
The HF equation accounts for the vapor phase nonidealities. The model is
based on chemical theory and assumes the formation of hexamers.
Species like HF that associate linearly behave as single species. For example,
they have a vapor pressure curve, like pure components. The component on
which a hypothetical unreacted system is based is often called the apparent
(or parent) component. Apparent components react to the true species.
Electrolyte Calculation in Physical Property Methods discusses apparent and
true species. Abbott and van Ness (1992) provide details and basic
thermodynamics of reactive systems.
The temperaturedependent hexamerization equilibrium constant, can fit the
experimentally determined association factors. The builtin functionality is:
(1)
The constants C
0
and C
1
are from Long et al. (1943), and C
2
and C
3
are set to
0. The correlation is valid between 270 and 330 K, and can be extrapolated to
about 370 K (cf. sec. 4). Different sets of constants can be determined by
experimental data regression.
Molar Volume Calculation
The nonideality of HF is often expressed using the association factor, f,
indicating the ratio of apparent number of species to the real number or
species. Assuming the ideal gas law for all true species in terms of (p, V, T)
behavior implies:
24 2 Thermodynamic Property Models
(2)
Where the true number of species is given by 1/f. The association factor is
easily determined from (p, V, T) experiments. For a critical evaluation of data
refer to Vanderzee and Rodenburg (1970).
If only one reaction is assumed for a mixture of HF and its associated species,
(refer to Long et al., 1943), then:
(3)
If p
1
represents the true partial pressure of the HF monomer, and p
6
represents the true partial pressure of the hexamer, then the equilibrium
constant is defined as:
(4)
The true total pressure is:
p = p
1
+ p
6
(5)
If all hexamer were dissociated, the apparent total pressure would be the
hypothetical pressure where:
p
a
= p
1
+ 6p
6
= p + 5p
6
(6)
When physical ideality is assumed, partial pressures and mole fractions are
proportional. The total pressure in equation 5 represents the true number of
species. The apparent total pressure from equation 6 represents the apparent
number of species:
(7)
Note that the outcome of equation 7 is independent of the assumption of
ideality. Equation 7 can be used to compute the number of true species 1/f
for a mixture containing HF, but the association factor is defined differently.
If p
1
and p
6
are known, the molar volume or density of a vapor containing HF
can be calculated using equations 2 and 7. The molar volume calculated is the
true molar volume for 1 apparent mole of HF. This is because the volume of 1
mole of ideal gas (the true molar volume per true number of moles) is always
equal to about 0.0224 m3/mol at 298.15 K.
True Mole Fraction (Partial Pressure) Calculation
If you assume the ideal gas law for a mixture containing HF, the apparent HF
mole fraction is:
(8)
2 Thermodynamic Property Models 25
The denominator of equation 8 is given by equation 6. The numerator (the
apparent partial pressure of HF) is the hypothetical partial pressure only if all
of the hexamer was dissociated. If you substitute equation 4, then equation 8
becomes:
(9)
K is known from Long et al., or can be regressed from (p,V,T) data. The
apparent mole fraction of HF, y
a
, is known to the user and the simulator, but
p
1
, or y = p
1
/p must also be known in order to calculate the thermodynamic
properties of the mixture. Equation 9 must be solved for p
1
.
Equation 9 can be written as a polynomial in p
1
of degree 6:
K(6  5y
a
)(p
1
)
6
+ p
1
 py
a
= 0 (9a)
A second order NewtonRaphson technique is used to determine p
1
. Then p
6
can be calculated by equation 5, and f is known (equation 7).
Gibbs Energy and Fugacity
The apparent fugacity coefficient is related to the true fugacity coefficient and
mole fractions:
(10)
Equation 10 represents a correction to the ideal mixing term of the fugacity.
The ratio of the true number of species to the apparent number of species is
similar to the correction applied in equation 2. Since the ideal gas law is
assumed, the apparent fugacity coefficient is given by the equation. All
variables on the right side are known.
(11)
For pure HF, y
a
= 1:
From the fugacity coefficient, the Gibbs energy departure of the mixture or
pure apparent components can be calculated:
(12)
(12a)
Enthalpy and Entropy
For the enthalpy departure, the heat of reaction is considered. For an
arbitrary gas phase reaction:
26 2 Thermodynamic Property Models
(13)
(14)
Where
i
*
is the pure component thermodynamic potential or molar Gibbs
energy of a component. Equation 4 represents the first two terms of the
general equation 14. The second or third equality relates the equilibrium
constant to the Gibbs energy of reaction, which is thus related to the enthalpy
of reaction:
(15)
All components are assumed to be ideal. The enthalpy departure is equal to
the heat of reaction, per apparent number of moles:
(16)
(17)
From the Gibbs energy departure and enthalpy departure, the entropy
departure can be calculated:
(18)
Temperature derivatives for the thermodynamic properties can be obtained
by straightforward differentiation.
Usage
The HF equationofstate should only be used for vapor phase calculations. It
is not suited for liquid phase calculations.
The HF equationofstate can be used with any activity coefficient model for
nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package
MHF2 is strongly recommended for aqueous mixtures (de Leeuw and
Watanasiri, 1993).
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
ESHFK/1 C
0
43.65
ESHFK/2 C
1
8910
ESHFK/3 C
2
0
ESHFK/4 C
3
0
References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53 119.
2 Thermodynamic Property Models 27
V. V. De Leeuw and S. Watanasiri, "Modelling Phase Equilibria and Enthalpies
of the System Water and Hydroflouric Acid Using an HF Equationofstate in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
presented at the 13th European Seminar on Applied Thermodynamics, June 9
12, CarryleRouet, France, 1993.
R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Flourides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182 187.
C. E. Vanderzee and W. WM. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461 478.
Ideal Gas
The ideal gas law (ideal gas equationofstate) combines the laws of Boyle
and GayLussac. It models a vapor as if it consisted of point masses without
any interactions. The ideal gas law is used as a reference state for equation
ofstate calculations, and can be used to model gas mixtures at low pressures
(without specific gas phase interactions).
The equation is:
p = RT / V
m
LeeKesler
This equationofstate model is based on the work of Lee and Kesler (1975).
In this equation, the volumetric and thermodynamic properties of fluids based
on the Curl and Pitzer approach (1958) have been analytically represented by
a modified BenedictWebbRubin equationofstate (1940). The model
calculates the molar volume, enthalpy departure, Gibbs free energy
departure, and entropy departure of a mixture at a given temperature,
pressure, and composition for either a vapor or a liquid phase. Partial
derivatives of these quantities with respect to temperature can also be
calculated.
Unlike the other equationofstate models, this model does not calculate
fugacity coefficients.
The compressibility factor and other derived thermodynamic functions of
nonpolar and slightly polar fluids can be adequately represented, at constant
reduced temperature and pressure, by a linear function of the acentric factor.
In particular, the compressibility factor of a fluid whose acentric factor is e, is
given by the following equation:
Z = Z
(0)
+ eZ
(1)
Where:
Z
(0)
= Compressibility factor of a simple fluid (e = 0)
Z
(1)
= Deviation of the compressibility factor of the real fluid from Z
(0)
28 2 Thermodynamic Property Models
Z
(0)
and Z
(1)
are assumed universal functions of the reduced temperature and
pressure.
Curl and Pitzer (1958) were quite successful in correlating thermodynamic
and volumetric properties using the above approach. Their application
employed tables of properties in terms of reduced temperature and pressure.
A significant weakness of this method is that the various properties (for
example, entropy departure and enthalpy departure) will not be exactly
thermodynamically consistent with each other. Lee and Kesler (1975)
overcame this drawback by an analytic representation of the tables with an
equationofstate. In addition, the range was extended by including new data.
In the LeeKesler implementation, the compressibility factor of any fluid has
been written in terms of a simple fluid and a reference as follows:
In the above equation both Z
(0)
and Z
(1)
are represented as generalized
equations of the BWR form in terms of reduced temperature and pressure.
Thus,
Equations for the enthalpy departure, Gibbs free energy departure, and
entropy departure are obtained from the compressibility factor using standard
thermodynamic relationships, thus ensuring thermodynamic consistency.
In the case of mixtures, mixing rules (without any binary parameters) are
used to obtain the mixture values of the critical temperature and pressure,
and the acentric factor.
This equation has been found to provide a good description of the volumetric
and thermodynamic properties of mixtures containing nonpolar and slightly
polar components.
Symbol Parameter Name Default Definition
T
c
TCLK TC Critical temperature
P
c
PCLK PC Critical pressure
e OMGLK OMEGA Acentric factor
References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
R. F. Curl and K.S. Pitzer, Ind. Eng. Chem., Vol. 50, (1958), p. 265.
B. I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975), p. 510.
LeeKeslerPlcker
The LeeKeslerPlcker equationofstate is the basis for the LKPLOCK
property method. This equationofstate applies to hydrocarbon systems that
2 Thermodynamic Property Models 29
include the common light gases, such as H
2
S and CO
2
. It can be used in gas
processing, refinery, and petrochemical applications.
The general form of the equation is:
Where:
The f
o
and f
R
parameters are functions of the BWR form. The f
o
parameter is
for a simple fluid, and f
R
is for reference fluid noctane.
The mixing rules are:
V
cm
=
=
e =
Z
m
=
Where:
V
cij
=
T
cij
=
Z
ci
=
k
ij
= k
ji
The binary parameter k
ij
is determined from phaseequilibrium data
regression, such as VLE data. The Aspen Physical Property System stores the
binary parameters for a large number of component pairs. These binary
parameters are used automatically with the LKPLOCK property method. If
binary parameters for certain component pairs are not available, they can be
estimated using builtin correlations. The correlations are designed for binary
interactions among the components CO, CO
2
, N
2
, H
2
, CH
4
alcohols and
hydrocarbons. If a component is not CO, CO
2
, N
2
, H
2
, CH
4
or an alcohol, it is
assumed to be a hydrocarbon.
Parameter
Name/
Element
SymbolDefault MDS Lower
Limit
Upper
Limit
Units
TCLKP T
ci
TC x 5.0 2000.0 TEMPERATURE
30 2 Thermodynamic Property Models
Parameter
Name/
Element
SymbolDefault MDS Lower
Limit
Upper
Limit
Units
PCLKP p
ci
PC x PRESSURE
VCLKP V
ci
VC x 0.001 3.5 MOLE
VOLUME
OMGLKP e
I
OMEGA x 0.5 2.0
LKPZC
Z
ci
fcn(e) (Method 1)
fcn(p
ci,
V
ci,
T
ci
)
(Method 2)
x 0.1 0.5
LKPKIJ
k
ij
fcn(T
ci
V
ci
/ T
cj
V
cj
) x 5.0 5.0
Method 1 is the default for LKPZC; Method 2 can be invoked by setting the
value of LKPZC equal to zero.
Binary interaction parameters LKPKIJ are available for a large number of
components in the Aspen Physical Property System.
References
B.I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975) p. 510; errata: AIChE J.,
Vol. 21, (1975) p. 1040.
V. Plcker, H. Knapp, and J.M. Prausnitz, Ind. Eng. Chem., Process Des. Dev.,
Vol. 17, (1978), p. 324.
NBS/NRC Steam Tables
The NBS/NRC Steam Tables are implemented like any other equationofstate
in the Aspen Physical Property System. These steam tables can calculate any
thermodynamic property of water. The tables form the basis of the
STEAMNBS and STMNBS2 property methods. There are no parameter
requirements. They are the most accurate steam tables in the Aspen Physical
Property System. The STMNBS2 model uses the same equations as
STEAMNBS but with different root search method. The STEAMNBS method is
recommended for use with the SRK, BWRS, MXBONNEL and GRAYSON2
property methods.
References
L. Haar, J.S. Gallagher, and J.H. Kell, "NBS/NRC Steam Tables," (Washington:
Hemisphere Publishing Corporation, 1984).
Nothnagel
The Nothnagel equationofstate calculates thermodynamic properties for the
vapor phase. It is used in property methods NRTLNTH, UNIQNTH, VANL
NTH, and WILSNTH. It is recommended for systems that exhibit strong vapor
phase association. The model incorporates the chemical theory of
2 Thermodynamic Property Models 31
dimerization to account for strong association and solvation effects, such as
those found in organic acids, like acetic acid. The equationofstate is:
Where:
b =
b
ij
=
nc = Number of components in the mixture
The chemical reaction for the general case of a mixture of dimerizing
components i and j is:
The chemical equilibrium constant for the dimerization reaction on pressure
basis K
p
is related to the true mole fractions and fugacity coefficients:
Where:
y
i
and y
j
= True mole fractions of monomers
y
ij
= True mole fraction of dimer
i
= True fugacity coefficient of component i
K
ij
= Equilibrium constant for the dimerization of i and j, on a
pressure basis
When accounting for chemical reactions, the number of true species n
t
in the
mixture changes. The true molar volume V/n
t
is calculated from the
equationofstate. Since both V and n
t
change in about the same proportion,
this number does not change much. However, the reported molar volume is
the total volume over the apparent number of species: V/n
a
. Since the
apparent number of species is constant and the total volume decreases with
association, the quantity V/n
a
reflects the apparent contraction in an
associating mixture.
The heat of reaction due to each dimerization can be calculated:
The heat of reaction for the mixed dimerization of components i and j is by
default the arithmetic mean of the heats of reaction for the dimerizations of
32 2 Thermodynamic Property Models
the individual components. Parameter is a small empirical correction
factor to this value:
The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles, is added to the molar enthalpy
departure:
The equilibrium constants can be computed using either builtin calculations
or parameters you entered.
 Builtin correlations:
The pure component parameters b, d, and p are stored in the Aspen
Physical Property System for many components.
Parameters you entered:
In this method, you enter A
i
, B
i
, C
i
, and D
i
on the Properties Parameters
Unary.TDependent form. The units for K
ii
is pressure
1
; use absolute units for
temperature. If you enter K
ii
and K
jj
, then K
ij
is computed from
If you enter A
i
, B
i
, C
i
, and D
i
, the equilibrium constants are computed using
the parameters you entered. Otherwise the equilibrium constants are
computed using builtin correlations.
Parameter
Name/Element
Symbol Default Lower
Limit
Upper Limit Units
TC T
ci
5.0 2000.0 TEMPERATURE
TB T
bi
4.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
NTHA/1 b
i
0.199 RT
ci
/ p
ci
0.01 1.0 MOLEVOLUME
NTHA/2 d
i
0.33 0.01 3.0
NTHA/3 p
i
0 0.0 1.0
NTHK/1 A
i
PRESSURE
NTHK/2 B
i
0 TEMPERATURE
NTHK/3 C
i
0 TEMPERATURE
NTHK/4 D
i
0 TEMPERATURE
NTHDDH 0
MOLE
ENTHALPY
For the following systems, the values given in Nothnagel et al., 1973 are
used by default:
 Methyl chloride/acetone
 Acetonitrile/acetaldehyde
 Acetone/chloroform
2 Thermodynamic Property Models 33
 Chloroform/diethyl amine
 Acetone/benzene
 Benzene/chloroform
 Chloroform/diethyl ether
 Chloroform/propyl formate
 Chloroform/ethyl acetate
 Chloroform/methyl acetate
 Chloroform/methyl formate
 Acetone/dichloro methane
 nButane/nperfluorobutane
 nPentane/nperfluoropentane
 nPentane/nperfluorohexane
References
K.H. Nothnagel, D. S. Abrams, and J.M. Prausnitz, "Generalized Correlation
for Fugacity Coefficients in Mixtures at Moderate Pressures," Ind. Eng. Chem.,
Process Des. Dev., Vol. 12, No. 1 (1973), pp. 25 35.
PengRobinson
The PengRobinson equationofstate is the basis for the PENGROB and PR
BM property methods. The model has been implemented with choices of
different alpha functions (see PengRobinson Alpha Functions) and has been
extended to include advanced asymmetric mixing rules.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
By default, the PENGROB property method uses the literature version of the
alpha function and mixing rules. The PRBM property method uses the
BostonMathias alpha function and standard mixing rules. These default
property methods are recommended for hydrocarbon processing applications
such as gas processing, refinery, and petrochemical processes. Their results
are comparable to those of the property methods that use the standard
RedlichKwongSoave equationofstate.
When advanced alpha function and asymmetric mixing rules are used with
appropriately obtained parameters, the PengRobinson model can be used to
accurately model polar, nonideal chemical systems. Similar capability is also
available for the SoaveRedlichKwong model.
The equation for the PengRobinson model is:
Where:
34 2 Thermodynamic Property Models
b =
c =
a = a
0
+a
1
a
0
=
(the standard quadratic mixing term, where k
ij
has
been made temperaturedependent)
k
ij
=
k
ij
= k
ji
a
1
(an additional, asymmetric term used to model
highly nonlinear systems)
l
ij
=
In general, .
a
i
=
b
i
=
c
i
=
For best results, the binary parameters k
ij
and l
ij
must be determined from
regression of phase equilibrium data such as VLE data. The Aspen Physical
Property System also has builtin k
ij
and l
ij
for a large number of component
pairs in the EOSLIT databank. These parameters are used automatically with
the PENGROB property method. Values in the databank can be different than
those used with other models such as SoaveRedlichKwong or Redlich
KwongSoave, and this can produce different results.
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng
Robinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPR) for a list of the option
codes.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
PRTC T
ci
TC x 5.0 2000.0 TEMPERATURE
PRPC p
ci
PC x 10
5
10
8
PRESSURE
OMGPR
e
i
OMEGA x 0.5 2.0
PRZRA z
RA
RKTZRA x
2 Thermodynamic Property Models 35
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
PRKBV/1 k
ij
(1)
0 x
PRKBV/2 k
ij
(2)
0 x TEMPERATURE
PRKBV/3 k
ij
(3)
0 x TEMPERATURE
PRKBV/4 T
lower
0 x TEMPERATURE
PRKBV/5 T
upper
1000 x TEMPERATURE
PRLIJ/1 l
ij
(1)
0 x
PRLIJ/2 l
ij
(2)
0 x TEMPERATURE
PRLIJ/3 l
ij
(3)
0 x TEMPERATURE
PRLIJ/4 T
lower
0 x TEMPERATURE
PRLIJ/5 T
upper
1000 x TEMPERATURE
References
D.Y. Peng and D. B. Robinson, "A New TwoConstant Equationofstate," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 3144.
Standard PengRobinson
The Standard PengRobinson equationofstate is the original formulation of
the PengRobinson equation of state with the standard alpha function (see
PengRobinson Alpha Functions). It is recommended for hydrocarbon
processing applications such as gas processing, refinery, and petrochemical
processes. Its results are comparable to those of the standard Redlich
KwongSoave equation of state.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The equation for this model is:
Where:
b =
a =
a
i
=
b
i
=
36 2 Thermodynamic Property Models
k
ij
=
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng
Robinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPRSTD) for a list of the option
codes.
For best results, the binary parameter k
ij
must be determined from regression
of phase equilibrium data such as VLE data. The Aspen Physical Property
System also has builtin k
ij
for a large number of component pairs in the EOS
LIT databank. These parameters are used automatically with the PENGROB
property method. Values in the databank can be different than those used
with other models such as SoaveRedlichKwong or RedlichKwongSoave,
and this can produce different results.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCPRS T
ci
TC x 5.0 2000.0 TEMPERATURE
PCPRS p
ci
PC x 10
5
10
8
PRESSURE
OMGPRS
e
i
OMEGA x 0.5 2.0
PRKBV/1 k
ij
(1)
0 x   
PRKBV/2 k
ij
(2)
0 x   TEMPERATURE
PRKBV/3 k
ij
(3)
0 x   TEMPERATURE
PRKBV/4 T
lower
0 x   TEMPERATURE
PRKBV/5 T
upper
1000 x   TEMPERATURE
References
D.Y. Peng and D. B. Robinson, "A New TwoConstant Equationofstate," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
PengRobinsonMHV2
This model uses the PengRobinson equationofstate for pure compounds.
The mixing rules are the predictive MHV2 rules. Several alpha functions can
be used in the PengRobinsonMHV2 equationofstate model for a more
accurate description of the pure component behavior. The pure component
behavior and parameter requirements are described in Standard Peng
Robinson, or in PengRobinson Alpha Functions.
The MHV2 mixing rules are an example of modified HuronVidal mixing rules.
A brief introduction is provided in HuronVidal Mixing Rules. For more details,
see MHV2 Mixing Rules.
2 Thermodynamic Property Models 37
Predictive SRK (PSRK)
This model uses the RedlichKwongSoave equationofstate for pure
compounds. The mixing rules are the predictive Holderbaum rules, or PSRK
method. Several alpha functions can be used in the PSRK equationofstate
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in
Standard RedlichKwongSoave and in Soave Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The PSRK method is an example of modified HuronVidal mixing rules. A brief
introduction is provided in HuronVidal Mixing Rules. For more details, see
Predictive SoaveRedlichKwongGmehling Mixing Rules.
PengRobinsonWongSandler
This model uses the PengRobinson equationofstate for pure compounds.
The mixing rules are the predictive WongSandler rules. Several alpha
functions can be used in the PengRobinsonWongSandler equationofstate
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in Peng
Robinson, and in PengRobinson Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The WongSandler mixing rules are an example of modified HuronVidal
mixing rules. A brief introduction is provided in HuronVidal Mixing Rules. For
more details see WongSandler Mixing Rules., this chapter.
RedlichKwong
The RedlichKwong equationofstate can calculate vapor phase
thermodynamic properties for the following property methods: NRTLRK,
UNIFAC, UNIFLL, UNIQRK, VANLRK, and WILSRK. It is applicable for
systems at low to moderate pressures (maximum pressure 10 atm) for which
the vaporphase nonideality is small. The HaydenO'Connell model is
recommended for a more nonideal vapor phase, such as in systems
containing organic acids. It is not recommended for calculating liquid phase
properties.
The equation for the model is:
p =
Where:
38 2 Thermodynamic Property Models
=
b =
a
i
=
b
i
=
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
References
O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An
Equationofstate. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1979), pp. 223 244.
RedlichKwongAspen
The RedlichKwongAspen equationofstate is the basis for the RKASPEN
property method. It can be used for hydrocarbon processing applications. It is
also used for more polar components and mixtures of hydrocarbons, and for
light gases at medium to high pressures.
The equation is the same as RedlichKwongSoave:
p =
A quadratic mixing rule is maintained for:
a =
An interaction parameter is introduced in the mixing rule for:
b =
For a
i
an extra polar parameter is used:
a
i
=
b
i
=
The interaction parameters are temperaturedependent:
2 Thermodynamic Property Models 39
k
a,ij
=
k
b,ij
=
For best results, binary parameters k
ij
must be determined from phase
equilibrium data regression, such as VLE data.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKA T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKA p
ci
PC x 10
5
10
8
PRESSURE
OMGRKA
e
i
OMEGA x 0.5 2.0
RKAPOL
q
i
0 x 2.0 2.0
RKAKA0 k
a,ij
0
0 x 5.0 5.0
RKAKA1 k
a,ij
1
0 x 15.0 15.0 TEMPERATURE
RKAKB0 k
b,ij
0
0 x 5.0 5.0
RKAKB1 k
b,ij
1
0 x 15.0 15.0 TEMPERATURE
References
Mathias, P.M., "A Versatile Phase Equilibrium Equationofstate", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 391.
RedlichKwongSoave
This is the standard RedlichKwongSoave equationofstate, and is the basis
for the RKSOAVE property method. It is recommended for hydrocarbon
processing applications, such as gasprocessing, refinery, and petrochemical
processes. Its results are comparable to those of the PengRobinson
equationofstate.
The equation is:
Where:
a
0
is the standard quadratic mixing term:
a
1
is an additional, asymmetric (polar) term:
40 2 Thermodynamic Property Models
b =
a
i
=
b
i
=
k
ij
= k
ji
; ;
The parameter a
i
is calculated according to the standard Soave formulation
(see Soave Alpha Functions, equations 1, 2, 3, 5, and 6).
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The model uses option codes which are described in SoaveRedlichKwong
Option Codes.
For best results, binary parameters k
ij
must be determined from phase
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has builtin k
ij
for a large number of component pairs in
the EOSLIT databank. These binary parameters are used automatically with
the RKSOAVE property method. Values of k
ij
in the databank can be different
than those used with other models such as SoaveRedlichKwong or Standard
PengRobinson, and this can produce different results.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKSS T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKSS p
ci
PC x 10
5
10
8
PRESSURE
OMRKSS
e
i
OMEGA x 0.5 2.0
RKSKBV/1 k
ij
(1)
0 x 5.0 5.0
RKSKBV/2 k
ij
(2)
0 x TEMPERATURE
RKSKBV/3 k
ij
(3)
0 x TEMPERATURE
RKSKBV/4 T
k,lower
0 x TEMPERATURE
RKSKBV/5 T
k,upper
1000 x TEMPERATURE
RKSLBV/1 l
ij
(1)
0 x
RKSLBV/2 l
ij
(2)
0 x TEMPERATURE
RKSLBV/3 l
ij
(3)
0 x TEMPERATURE
RKSLBV/4 T
l,lower
0 x TEMPERATURE
RKSLBV/5 T
l,upper
1000 x TEMPERATURE
2 Thermodynamic Property Models 41
References
G. Soave, "Equilibrium Constants for Modified RedlichKwong Equationof
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equationofstate," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 1955.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich
KwongSoave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
RedlichKwongSoaveBostonMathias
The RedlichKwongSoaveBostonMathias equationofstate is the basis for
the RKSBM property method. It is the RedlichKwongSoave equationof
state with the BostonMathias alpha function (see Soave Alpha Functions). It
is recommended for hydrocarbon processing applications, such as gas
processing, refinery, and petrochemical processes. Its results are comparable
to those of the PengRobinsonBostonMathias equationofstate.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The equation is:
p =
Where:
a
0
is the standard quadratic mixing term:
a
1
is an additional, asymmetric (polar) term:
b =
a
i
=
b
i
=
k
ij
= k
ji
42 2 Thermodynamic Property Models
; ;
The parameter a
i
is calculated by the standard Soave formulation at
supercritical temperatures. If the component is supercritical, the Boston
Mathias extrapolation is used (see Soave Alpha Functions).
The model uses option codes which are described in SoaveRedlichKwong
Option Codes.
For best results, binary parameters k
ij
must be determined from phase
equilibrium data regression (for example, VLE data).
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKS T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKS p
ci
PC x 10
5
10
8
PRESSURE
OMGRKS
e
i
OMEGA x 0.5 2.0
RKSKBV/1 k
ij
(1)
0 x 5.0 5.0
RKSKBV/2 k
ij
(2)
0 x TEMPERATURE
RKSKBV/3 k
ij
(3)
0 x TEMPERATURE
RKSKBV/4 T
k,lower
0 x TEMPERATURE
RKSKBV/5 T
k,upper
1000 x TEMPERATURE
RKSLBV/1 l
ij
(1)
0 x
RKSLBV/2 l
ij
(2)
0 x TEMPERATURE
RKSLBV/3 l
ij
(3)
0 x TEMPERATURE
RKSLBV/4 T
l,lower
0 x TEMPERATURE
RKSLBV/5 T
l,upper
1000 x TEMPERATURE
References
G. Soave, "Equilibrium Constants for Modified RedlichKwong Equationof
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 1203.
RedlichKwongSoaveWongSandler
This equationofstate model uses the RedlichKwongSoave equationofstate
for pure compounds. The predictive WongSandler mixing rules are used.
Several alpha functions can be used in the RedlichKwongSoaveWong
Sandler equationofstate model for a more accurate description of the pure
component behavior. The pure component behavior and parameter
requirements are described in Standard RedlichKwongSoave, and in Soave
Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The WongSandler mixing rules are an example of modified HuronVidal
mixing rules. A brief introduction is provided in HuronVidal Mixing Rules. For
more details, see WongSandler Mixing Rules.
2 Thermodynamic Property Models 43
RedlichKwongSoaveMHV2
This equationofstate model uses the RedlichKwongSoave equationofstate
for pure compounds. The predictive MHV2 mixing rules are used. Several
alpha functions can be used in the RKSoaveMHV2 equationofstate model
for a more accurate description of the pure component behavior. The pure
component behavior and its parameter requirements are described in
Standard RedlichKwongSoave, and in Soave Alpha Functions.
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The MHV2 mixing rules are an example of modified HuronVidal mixing rules.
A brief introduction is provided in HuronVidal Mixing Rules. For more details,
see MHV2 Mixing Rules.
SchwartzentruberRenon
The SchwartzentruberRenon equationofstate is the basis for the SRPOLAR
property method. It can be used to model chemically nonideal systems with
the same accuracy as activity coefficient property methods, such as the
WILSON property method. This equationofstate is recommended for highly
nonideal systems at high temperatures and pressures, such as in methanol
synthesis and supercritical extraction applications.
The equation for the model is:
p =
Where:
a =
b =
c =
a
i
=
b
i
=
c
i
=
k
a,ij
=
l
ij
=
44 2 Thermodynamic Property Models
k
b,ij
=
k
a,ij
= k
a,ji
l
ij
= l
ji
k
b,ij
= k
b,ji
The binary parameters k
a,ij
, k
b,ij
, and l
ij
are temperaturedependent. In most
cases, k
a,ij
0
and l
ij
0
are sufficient to represent the system of interest.
VLE calculations are independent of c. However, c does influence the fugacity
values and can be adjusted to (liquid) molar volumes. For a wide temperature
range, adjust c
io
to the molar volume at 298.15K or at boiling temperature.
Warning: Using c
1i
and c
2i
can cause anomalous behavior in enthalpy and
heat capacity. Their use is strongly discouraged.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKU T
ci
TC x 5.0 2000.0 TEMPERATURE
PCRKU p
ci
PC x 105 108 PRESSURE
OMGRKU
e
i
OMEGA x 0.5 2.0
RKUPP0 q
0i
x
RKUPP1 q
1i
0 x
RKUPP2 q
2i
0 x
RKUC0 c
0i
0 x
RKUC1 c
1i
0 x
RKUC2 c
2i
0 x
RKUKA0 k
a,ij
0
0 x
RKUKA1 k
a,ij
1
0 x TEMPERATURE
RKUKA2 k
a,ij
2
0 x TEMPERATURE
RKULA0 l
ij
0
0 x
RKULA1 l
ij
1
0 x TEMPERATURE
RKULA2 l
ij
2
0 x TEMPERATURE
RKUKB0 k
b,ij
0
0 x
RKUKB1 k
b,ij
1
0 x TEMPERATURE
RKUKB2 k
b,ij
2
0 x TEMPERATURE
Absolute temperature units are assumed for k
a,ij
2
, l
ij
2
, and k
b,ij
2
.
For polar components (dipole moment >> 0), if you do not enter q
0i
, the
system estimates q
0i
, q
1i
, q
2i
from vapor pressures using the Antoine vapor
pressure model.
If you do not enter at least one of the binary parameters k
a,ij
0
, k
a,ij
2
, l
ij
0
,
l
ij
2
, k
b,ij
0
, or k
b,ij
2
the system estimates k
a,ij
0
, k
a,ij
2
, l
ij
0
, and l
ij
2
from the UNIFAC
or Hayden O'Connell models.
References
G. Soave, "Equilibrium Constants for Modified RedlichKwong Equationof
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196  1203.
2 Thermodynamic Property Models 45
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic EquationofState," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 1955.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich
KwongSoave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
SoaveRedlichKwong
The SoaveRedlichKwong equationofstate is the basis of the SRK property
method. This model is based on the same equation of state as the Redlich
KwongSoave model. However, this model has several important differences.
 A volume translation concept introduced by Peneloux and Rauzy is used to
improve molar liquid volume calculated from the cubic equation of state.
 Improvement in water properties is achieved by using the NBS Steam
Table.
 Improvement in speed of computation for equation based calculation is
achieved by using composition independent fugacity.
 Optional KabadiDanner mixing rules for improved phase equilibrium
calculations in waterhydrocarbon systems (see SRKKabadiDanner)
 Optional Mathias alpha function
Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
This equationofstate can be used for hydrocarbon systems that include the
common light gases, such as H
2
S, CO
2
and N
2
.
The form of the equationofstate is:
Where:
a
0
is the standard quadratic mixing term:
Where:
;
a
1
is an additional, asymmetric (polar) term:
46 2 Thermodynamic Property Models
Where:
; ;
The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables. The total properties are molefraction
averages of these values with the properties calculated by the equation of
state for other components. Fugacity coefficient is not affected.
For best results, the binary parameter k
ij
must be determined from phase
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has builtin k
ij
for a large number of component pairs in
the SRKASPEN databank. These parameters are used automatically with the
SRK property method. Values of k
ij
in the databank can be different than
those used with other models such as Standard RedlichKwongSoave or
Standard RedlichKwongSoave, and this can produce different results.
The model uses option codes which are described in SoaveRedlichKwong
Option Codes.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
SRKTC T
ci
TC x 5.0 2000.0 TEMPERATURE
SRKPC p
ci
PC x 10
5
10
8
PRESSURE
SRKOMG
e
i
OMEGA x 0.5 2.0
SRKZRA z
RA
RKTZRA x
SRKKIJ/1 k
ij
(1)
0 x
SRKKIJ/2 k
ij
(2)
0 x TEMPERATURE
SRKKIJ/3 k
ij
(3)
0 x TEMPERATURE
SRKKIJ/4 T
lower
0 x TEMPERATURE
SRKKIJ/5 T
upper
1000 x TEMPERATURE
SRKLIJ/1 l
ij
(1)
0 x
SRKLIJ/2 l
ij
(2)
0 x TEMPERATURE
SRKLIJ/3 l
ij
(3)
0 x TEMPERATURE
SRKLIJ/4 T
lower
0 x TEMPERATURE
SRKLIJ/5 T
upper
1000 x TEMPERATURE
2 Thermodynamic Property Models 47
References
G. Soave, "Equilibrium Constants for Modified RedlichKwong Equationof
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196  1203.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich
KwongSoave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 723.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 3144.
SRKKabadiDanner
The SRKKabadiDanner property model uses the SRK equationofstate with
improved phase equilibrium calculations for mixtures containing water and
hydrocarbons. These improvements are achieved by using the KabadiDanner
mixing rules.
The form of the equationofstate is:
Where:
a
0
is the standard quadratic mixing term:
Where:
;
The best values of k
wj
(w = water) were obtained from experimental data.
Results are given for seven homologous series.
Best Fit Values of k
wj
for Different Homologous Series
with Water
Homologous series k
wj
Alkanes 0.500
Alkenes 0.393
Dialkenes 0.311
Acetylenes 0.348
Naphthenes 0.445
Cycloalkenes 0.355
Aromatics 0.315
a
KD
is the KabadiDanner term for water:
48 2 Thermodynamic Property Models
Where:
G
i
is the sum of the group contributions of different groups which make up a
molecule of hydrocarbon i.
g
l
is the group contribution parameter for groups constituting hydrocarbons.
Groups Constituting Hydrocarbons and Their Group
Contribution Parameters
Group l g
l
, atm m
6
x 10
5
CH4 1.3580
CH3 0.9822
CH2 1.0780
> CH 0.9728
> C < 0.8687
CH2 (cyclic) 0.7488
> CH (cyclic) 0.7352
CH = CH (cyclic) 0.6180
CH2 = CH2 1.7940
CH2 = CH 1.3450
CH2 = C< 0.9066
CH CH 1.6870
CH C 1.1811
CH = 0.5117
> C = (aromatic) 0.3902
This value is obtained from very little data. Might not be reliable.
The model uses option codes which are described in SoaveRedlichKwong
Option Codes.
SRKKabadiDanner uses the same parameters as SRK, with added
interaction parameters. Do not specify values for the SRKLIJ parameters
when using SRKKD.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
SRKTC T
ci
TC x 5.0 2000.0 TEMPERATURE
SRKPC p
ci
PC x 10
5
10
8
PRESSURE
SRKOMG e
i
OMEGA x 0.5 2.0
SRKWF G
i
0 x
2 Thermodynamic Property Models 49
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
SRKZRA z
RA
RKTZRA x
SRKKIJ/1 k
ij
(1)
0 x
SRKKIJ/2 k
ij
(2)
0 x TEMPERATURE
SRKKIJ/3 k
ij
(3)
0 x TEMPERATURE
SRKKIJ/4 T
lower
0 x TEMPERATURE
SRKKIJ/5 T
upper
0 x TEMPERATURE
References
V. Kabadi and R. P. Danner, "A Modified SoaveRedlichKwong Equation of
State for WaterHydrocarbon Phase Equilibria", Ind. Eng. Chem. Process Des.
Dev., Vol. 24, No. 3, (1985), pp. 537541.
SRKML
The SRKML property model is the same as the standard SoaveRedlich
Kwong model with two exceptions:
 k
ij
may not equal k
ji
; they are unsymmetric, and a different set of
parameters are used, as shown below.
 The l
ij
are calculated from the equation l
ij
= k
ji
 k
ij
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
SRKTCML T
ci
TC x 5.0 2000.0 TEMPERATURE
SRKPCML p
ci
PC x 10
5
10
8
PRESSURE
SRKOMGML
e
i
OMEGA x 0.5 2.0
SRKZRAML z
RA
RKTZRA x
SRKKIJML/1 k
ij
(1)
0 x
SRKKIJML/2 k
ij
(2)
0 x TEMPERATURE
SRKKIJML/3 k
ij
(3)
0 x TEMPERATURE
SRKKIJML/4 T
lower
0 x TEMPERATURE
SRKKIJML/5 T
upper
1000 x TEMPERATURE
VPA/IKCAPE EquationofState
The VPA/IKCAPE equation of state is similar to the HF equation of state but
allows dimerization, tetramerization and hexamerization to occur
simultaneously. The main assumption of the model is that only molecular
association causes the gas phase nonideality. Attractive forces between the
molecules and the complexes are neglected.
There are three kinds of associations, which can be modeled:
 Dimerization (examples: formic acid, acetic acid)
50 2 Thermodynamic Property Models
 Tetramerization (example: acetic acid)
 Hexamerization (example: hydrogen fluoride)
To get the largest possible flexibility of the model all these kinds of
association can occur simultaneously, for example, in a mixture containing
acetic acid and HF. Up to five components can associate, and any number of
inert components are allowed. This is the only difference between this model
and the HF equation of state, which account only the hexamerization of HF.
Symbols
In the following description, these symbols are used:
y
i
= Apparent concentration
z
in
= True concentration, for component i and degree of
association n=1, 2, 4, 6
z
Mij
= True concentration of crossdimers of components i
and j, for i,j 1 to 5.
p
0
= Reference pressure
k = Number of components
Association Equilibria
Every association equilibrium reaction
(1)
(2)
is described by the equilibrium constants
(3)
(4)
By setting
(5)
(6)
their temperature dependence can be reproduced.
To evaluate the true concentration of every complex z
in
, the following
nonlinear systems of equations are to be solved:
2 Thermodynamic Property Models 51
Total mass balance:
The sum of true concentrations is unity.
(7)
Mass balance for every component i>1:
The ratio of the monomers of each component i>1 and component i=1
occurring in the various complexes must be equal to the ratio of their
apparent concentrations.
(8)
Thus, a system of k nonlinear equations for k unknowns z
i1
has been
developed. After having solved it, all the z
in
and z
Mij
can be determined using
equations (3, 4). This is the main step to evaluate all the properties needed
for a calculation.
Specific Volume of the Gas Phase
The compressibility factor is defined by the ratio between the number of
complexes and the number of monomers in the complexes.
(9)
The compressibility factor itself is
(10)
Fugacity Coefficient
As is wellknown from thermodynamics, the fugacity coefficient can be
calculated by
52 2 Thermodynamic Property Models
(11)
Isothermal Enthalpy Departure
According to the ASPEN enthalpy model, an equation of state must supply an
expression to compute the isothermal molar enthalpy departure between zero
pressure and actual pressure. In the following section this enthalpy
contribution per mole monomers is abbreviated by Ah
a
.
Taking this sort of gas phase nonideality into account, the specific enthalpy
per mole can be written as
(12)
with
(13)
to evaluate Ah
a
, a mixture consisting of N monomers integrated in the
complexes is considered. The quota of monomers i being integrated in a
complex of degree n is given by
(14)
and
(16)
respectively. For the reactions mentioned above:
(1)
(2)
the enthalpies of reaction are
(17)
(18)
as the van't Hoff equation
(19)
2 Thermodynamic Property Models 53
holds for this case.
For each monomer being integrated in a complex of degree n, its contribution
to the enthalpy departure is Ah
in
/ n or Ah
Mij
/ 2, respectively. Hence, Ah
a
can
easily be derived by
(20)
Isothermal entropy and Gibbs energy departure:
A similar expression for Ag
a
should hold as it does for the enthalpy departure
(eq. 20):
(21)
using
(22)
and
(23)
(24)
Using the association model, more different species occur than can be
distinguished. Thus, the equivalent expression for the entropy of mixing
should be written with the true concentrations. As eq. 24 refers to 1 mole
monomers, the expression should be weighted by the compressibility factor
representing the true number of moles. The new expression is
(25)
For Ag
a
we obtain
(26)
and, analogously,
(27)
54 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DMER/1 A
i2
0 X
DMER/2 B
i2
0 X TEMPERATURE
TMER/1 A
i4
0 X
TMER/2 B
i4
0 X TEMPERATURE
HMER/1 A
i6
0 X
HMER/2 B
i6
0 X TEMPERATURE
References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53119.
V. V. De Leeuw and S. Watanasiri, "Modeling Phase Equilibria and Enthalpies
of the System Water and Hydrofluoric Acid Using an HF Equationofstate in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
Presented at the 13th European Seminar on Applied Thermodynamics, June
912, CarryleRouet, France, 1993.
R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Fluorides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182187.
C. E. Vanderzee and W. Wm. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461478.
PengRobinson Alpha Functions
The pure component parameters for the PengRobinson equationofstate are
calculated as follows:
(1)
(2)
These expressions are derived by applying the critical constraints to the
equationofstate under these conditions:
(3)
The parameter o is a temperature function. It was originally introduced by
Soave in the RedlichKwong equationofstate. This parameter improves the
correlation of the pure component vapor pressure.
2 Thermodynamic Property Models 55
Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
This approach was also adopted by Peng and Robinson:
(4)
Equation 3 is still represented. The parameter m
i
can be correlated with the
acentric factor:
(5)
Equations 1 through 5 are the standard PengRobinson formulation. The
PengRobinson alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCPR T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR p
ci
PC X 10
5
10
8
PRESSURE
OMGPR
e
i
OMEGA X 0.5 2.0
BostonMathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 4 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and o reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(6)
With
=
=
Where m
i
is computed by equation 5, and equation 4 is used for subcritical
temperatures. Additional parameters are not needed.
Extended GibbonsLaughton Alpha Function
The extended GibbonsLaughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.
56 2 Thermodynamic Property Models
Where T
r
is the reduced temperature; X
i
, Y
i
and Z
i
are substance dependent
parameters.
This function is equivalent to the standard PengRobinson alpha function if
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
PRGLP/1 X X
PRGLP/2 Y 0 X
PRGLP/3 Z 0 X
PRGLP/4 n 2 X
PRGLP/5 T
lower
0 X TEMPERATURE
PRGLP/6 T
upper
1000 X TEMPERATURE
Twu Generalized Alpha Function
The Twu generalized alpha function is a theoreticallybased function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > T
c
) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.
Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For PengRobinson equation of state:
Subcritical T Supercritical T
L
(0)
0.272838 0.373949
M
(0)
0.924779 4.73020
N
(0)
1.19764 0.200000
L
(1)
0.625701 0.0239035
M
(1)
0.792014 1.24615
N
(1)
2.46022 8.000000
Twu Alpha Function
The Twu alpha function is a theoreticallybased function that is currently
recognized as the best available alpha function. It behaves better than other
functions at supercritical conditions (T > T
c
).
2 Thermodynamic Property Models 57
Where the L, M, and N are substancedependent parameters that must be
determined from regression of purecomponent vapor pressure data or other
data such as liquid heat capacity.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
PRTWUP/1 L X
PRTWUP/2 M 0 X
PRTWUP/3 N 0 X
MathiasCopeman Alpha Function
This is an extension of the PengRobinson alpha function which provides a
more accurate fit of vapor pressure for polar compounds.
(7)
For c
2,i
= 0 and c
3,i
= 0, this expression reduces to the standard Peng
Robinson formulation if c
2,i
= m
i
. You can use vapor pressure data if the
temperature is subcritical to regress the constants. If the temperature is
supercritical, c
2,i
and c
3,i
are set to 0.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCPR T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR p
ci
PC X 10
5
10
8
PRESSURE
PRMCP/1 c
1,i
X
PRMCP/2 c
2,i
0 X
PRMCP/3 c
3,i
0 X
SchwartzentruberRenonWatanasiri Alpha Function
The SchwartzentruberRenonWatanasiri alpha function is:
(8)
Where m
i
is computed by equation 5. The polar parameters p
1,i
, p
2,i
and p
3,i
are comparable with the c parameters of the MathiasCopeman expression.
Equation 8 reduces to the standard PengRobinson formulation if the polar
parameters are zero. Equation 8 is used only for belowcritical temperatures.
For abovecritical temperatures, the BostonMathias extrapolation is used.
Use equation 6 with:
(9)
(10)
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCPR T
ci
TC X 5.0 2000.0 TEMPERATURE
PCPR p
ci
PC X 10
5
10
8
PRESSURE
58 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
OMGPR
e
i
OMEGA X 0.5 2.0
PRSRP/1 X
PRSRP/2 0 X
PRSRP/3 0 X
Use of Alpha Functions
The alpha functions in PengRobinsonbased equationofstate models is
provided in the following table. You can verify and change the value of
possible option codes on the Properties  Property Methods  Model form.
Alpha function Model name First Option code
Standard Peng Robinson ESPRSTD0, ESPRSTD 1
Standard PR/
BostonMathias
ESPR0, ESPR
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
0
0
0
Extended Gibbons
Laughton
ESPR0, ESPR 2
Twu Generalized alpha
function
ESPR0, ESPR 3
Twu alpha function ESPR0, ESPR 4
MathiasCopeman ESPRWS0, ESPRWS
ESPRV20, ESPRV2
2
2
Schwartzentruber
Renon
Watanasiri
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
3 (default)
3 (default)
References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a ThirdGeneration Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(1721 March 1980) pp. 823849.
D.Y. Peng and D.B. Robinson, "A New TwoConstant Equationofstate," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 5964.
P.M. Mathias and T.W. Copeman, "Extension of the PengRobinson Equation
ofstate To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept",Fluid Phase Eq., Vol. 13, (1983), p. 91.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "Kvalues for NonIdeal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118124.
G. Soave, "Equilibrium Constants for a Modified RedlichKwong Equationof
state," Chem Eng. Sci., Vol. 27, (1972), pp. 11961203.
C.H. Twu, J. E. Coon, and J.R. Cunningham, "A New Cubic Equation of State,"
Fluid Phase Equilib., Vol. 75, (1992), pp. 6579.
2 Thermodynamic Property Models 59
C.H. Twu, D. Bluck, J.R. Cunningham, and J.E. Coon, "A Cubic Equation of
State with a New Alpha Function and a New Mixing Rule," Fluid Phase Equilib.,
Vol. 69, (1991), pp. 3350.
Soave Alpha Functions
The pure component parameters for the RedlichKwong equationofstate are
calculated as:
(1)
(2)
These expressions are derived by applying the critical constraint to the
equationofstate under these conditions:
(3)
Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
In the RedlichKwong equationofstate, alpha is:
(4)
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
Soave Modification
The parameter o
i
is a temperature function introduced by Soave in the
RedlichKwong equationofstate to improve the correlation of the pure
component vapor pressure:
(5)
Equation 3 still holds. The parameter m
i
can be correlated with the acentric
factor:
(6)
Equations 1, 2, 3, 5 and 6 are the standard RedlichKwongSoave
formulation. The Soave alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.
60 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKS T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKS p
ci
PC X 10
5
10
8
PRESSURE
OMGRKS e
i
OMEGA X 0.5 2.0
BostonMathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 5 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(7)
With
d
i
=
c
i
=
Where:
m
i
= Computed by equation 6
Equation 5 = Used for subcritical temperatures
Additional parameters are not needed.
Mathias Alpha Function
This is an extension of the Soave alpha function which provides a more
accurate fit of vapor pressure for polar compounds.
(8)
For q
i
=0, equation 8 reduces to the standard RedlichKwongSoave
formulation, equations 5 and 6. For temperatures above critical, the Boston
Mathias extrapolation is used, that is, equation 7 with:
(9)
(10)
The Mathias alpha function is used in the RedlichKwongAspen model, which
is the basis for the RKASPEN property method. This alpha function is also
available as an option for SRK, SRKKD, SRKML, RKSOAVE, and RKSBM.
See SoaveRedlichKwong Option Codes for more information.
2 Thermodynamic Property Models 61
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKA T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKA p
ci
PC X 10
5
10
8
PRESSURE
OMGRKA e
i
OMEGA X 0.5 2.0
q
i
X 2.0 2.0
RKAPOL for RedlichKwongAspen, SRKPOL for SRK and SRKKD, SRKMLP for
SRKML, RKSPOL for RKSBM, or RKSSPO for RKSOAVE.
Extended Mathias Alpha Function
An extension of the Mathias approach is:
(11)
Where m
i
is computed by equation 6. If the polar parameters p
1,i
, p
2,i
and p
3,i
are zero, equation 11 reduces to the standard RedlichKwongSoave
formulation. You can use vapor pressure data to regress the constants if the
temperature is subcritical. Equation 11 is used only for temperatures below
critical.
The BostonMathias extrapolation is used for temperatures above critical, that
is, with:
(12)
(13)
This alpha function is used in the RedlichKwongUNIFAC model which is the
basis for the SRPOLAR property method.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKU T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKU p
ci
PC X 10
5
10
8
PRESSURE
OMGRKU e
i
OMEGA X 0.5 2.0
RKUPP0 p
1,i
X
RKUPP1 p
2,i
0 X
RKUPP2 p
3,i
0 X
MathiasCopeman Alpha Function
The MathiasCopeman alpha function is suitable for use with both polar and
nonpolar components. It has the flexibility to fit the vapor pressure of most
substances from the triple point to the critical point.
(14)
For c
2,i
=0 and c
3,i
=0 this expression reduces to the standard RedlichKwong
Soave formulation if c
1,i
=m
i
. If the temperature is subcritical, use vapor
62 2 Thermodynamic Property Models
pressure data to regress the constants. If the temperature is supercritical, set
c
2,i
and c
3,i
to 0.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKS T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKS p
ci
PC X 10
5
10
8
PRESSURE
RKSMCP/1 c
1,i
X
RKSMCP/2 c
2,i
0 X
RKSMCP/3 c
3,i
0 X
SchwartzentruberRenonWatanasiri Alpha Function
The SchwartzentruberRenonWatanasiri alpha function is:
(15)
Where m
i
is computed by equation 6 and the polar parameters p
1,i
, p
2,i
and p
3,i
are comparable with the c parameters of the MathiasCopeman expression.
Equation 15 reduces to the standard RedlichKwongSoave formulation if the
polar parameters are zero. Equation 15 is very similar to the extended
Mathias equation, but it is easier to use in data regression. It is used only for
temperatures below critical. The BostonMathias extrapolation is used for
temperatures above critical, that is, use equation 7 with:
(16)
(17)
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TCRKS T
ci
TC X 5.0 2000.0 TEMPERATURE
PCRKS p
ci
PC X 10
5
10
8
PRESSURE
OMGRKS e
i
OMEGA X 0.5 2.0
RKSSRP/1 p
1,i
X
RKSSRP/2 p
2,i
0 X
RKSSRP/3 p
3,i
0 X
Extended GibbonsLaughton Alpha Function
The extended GibbonsLaughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.
Where T
r
is the reduced temperature; X
i
, Y
i
and Z
i
are substance dependent
parameters.
2 Thermodynamic Property Models 63
This function is equivalent to the standard Soave alpha function if
This function is not intended for use in supercritical conditions. To avoid
predicting negative alpha, when T
ri
>1 the BostonMathias alpha function is
used instead.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
RKSGLP/1 X X
RKSGLP/2 Y 0 X
RKSGLP/3 Z 0 X
RKSGLP/4 n 2 X
RKSGLP/5 T
lower
0 X TEMPERATURE
RKSGLP/6 T
upper
1000 X TEMPERATURE
Twu Generalized Alpha Function
The Twu generalized alpha function is a theoreticallybased function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > T
c
) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.
Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For SoaveRedlichKwong:
Subcritical T Supercritical T
L
(0)
0.544000 0.379919
M
(0)
1.01309 5.67342
N
(0)
0.935995 0.200000
L
(1)
0.544306 0.0319134
M
(1)
0.802404 1.28756
N
(1)
3.10835 8.000000
Use of Alpha Functions
The use of alpha functions in SoaveRedlichKwong based equationofstate
models is given in the following table. You can verify and change the value of
possible option codes on the Properties  Property Methods  Models
sheet.
Alpha Function Model Name First Option Code
64 2 Thermodynamic Property Models
Alpha Function Model Name First Option Code
original RK ESRK0, ESRK
standard RKS ESRKSTD0, ESRKSTD
standard RKS/BostonMathias ESRKS0, ESRKS
ESRKSWS0, ESRKSWS
ESRKSV10, ESRKV1
ESRKSV20, ESRKSV2
1
1
1
Mathias/BostonMathias ESRKA0, ESRKA
Extended Mathias/Boston
Mathias
ESRKU0, ESRKU
MathiasCopeman ESRKSW0, ESRKSW
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
2
2
2
SchwartzentruberRenon
Watanasiri
ESPRWS0, ESPRWS
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
3 (default)
3 (default)
3 (default)
Twu generalized ESRKSTD0, ESRKSTD,
ESRKS, ESRKS0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
5
GibbonsLaughton with Patel
extension
ESRKSTD0, ESRKSTD,
ESRKS, ESRKS0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
3
Mathias for T < Tc; Boston
Mathias for T > Tc
ESRKSTD0, ESRKSTD,
ESRKS, ESRKS0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
4
References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a ThirdGeneration Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(1721 March 1980), pp. 823849.
P. M. Mathias, "A Versatile Phase Equilibrium Equationofstate", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385391.
P.M. Mathias and T.W. Copeman, "Extension of the PengRobinson Equation
ofstate To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept", Fluid Phase Eq., Vol. 13, (1983), p. 91.
O. Redlich and J. N. S. Kwong, "On the Thermodynamics of Solutions V. An
Equationofstate. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1949), pp. 223244.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equationofstate," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 10491055.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "Kvalues for NonIdeal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118124.
G. Soave, "Equilibrium Constants for a Modified RedlichKwong Equationof
state," Chem Eng. Sci., Vol. 27, (1972), pp. 11961203.
2 Thermodynamic Property Models 65
C.H. Twu, W.D. Sim, and V. Tassone, "Getting a Handle on Advanced Cubic
Equations of State", Chemical Engineering Progress, Vol. 98 #11 (November
2002) pp. 5865.
HuronVidal Mixing Rules
Huron and Vidal (1979) used a simple thermodynamic relationship to equate
the excess Gibbs energy to expressions for the fugacity coefficient as
computed by equations of state:
(1)
Equation 1 is valid at any pressure, but cannot be evaluated unless some
assumptions are made. If Equation 1 is evaluated at infinite pressure, the
mixture must be liquidlike and extremely dense. It can be assumed that:
(2)
(3)
Using equations 2 and 3 in equation 1 results in an expression for a/b that
contains the excess Gibbs energy at an infinite pressure:
(4)
Where:
(5)
The parameters
1
and
2
depend on the equationofstate used. In general a
cubic equationofstate can be written as:
(6)
Values for
1
and
2
for the PengRobinson and the SoaveRedlichKwong
equations of state are:
Equationofstate
1
2
PengRobinson
RedlichKwongSoave 1 0
This expression can be used at any pressure as a mixing rule for the
parameter. The mixing rule for b is fixed by equation 3. Even when used at
other pressures, this expression contains the excess Gibbs energy at infinite
pressure. You can use any activity coeffecient model to evaluate the excess
Gibbs energy at infinite pressure. Binary interaction coefficients must be
regressed. The mixing rule used contains as many binary parameters as the
activity coefficient model chosen.
66 2 Thermodynamic Property Models
This mixing rule has been used successfully for polar mixtures at high
pressures, such as systems containing light gases. In theory, any activity
coefficient model can be used. But the NRTL equation (as modified by Huron
and Vidal) has demonstrated better performance.
The HuronVidal mixing rules combine extreme flexibility with thermodynamic
consistency, unlike many other molefractiondependent equationofstate
mixing rules. The HuronVidal mixing rules do not allow flexibility in the
description of the excess molar volume, but always predict reasonable excess
volumes.
The HuronVidal mixing rules are theoretically incorrect for low pressure,
because quadratic mole fraction dependence of the second virial coefficient (if
derived from the equationofstate) is not preserved. Since equations of state
are primarily used at high pressure, the practical consequences of this
drawback are minimal.
The Gibbs energy at infinite pressure and the Gibbs energy at an arbitrary
high pressure are similar. But the correspondence is not close enough to
make the mixing rule predictive.
There are several methods for modifying the HuronVidal mixing rule to make
it more predictive. The following three methods are used in Aspen Physical
Property System equationofstate models:
 The modified HuronVidal mixing rule, second order approximation
(MHV2)
 The Predictive SRK Method (PSRK)
 The WongSandler modified HuronVidal mixing rule (WS)
These mixing rules are discussed separately in the following sections. They
have major advantages over other compositiondependent equationofstate
mixing rules.
References
M. J. Huron and J. Vidal, "New Mixing Rules in Simple Equations of State for
representing Vapourliquid equilibria of strongly nonideal mixtures," Fluid
Phase Eq., Vol. 3, (1979), pp. 255271.
MHV2 Mixing Rules
Dahl and Michelsen (1990) use a thermodynamic relationship between excess
Gibbs energy and the fugacity computed by equations of state. This
relationship is equivalent to the one used by Huron and Vidal:
(1)
The advantage is that the expressions for mixture and pure component
fugacities do not contain the pressure. They are functions of compacity V/b
and o:
2 Thermodynamic Property Models 67
(2)
Where:
(3)
and
(4)
With:
(5)
The constants
1
and
2
, which depend only on the equationofstate (see
HuronVidal Mixing Rules) occur in equations 2 and 4.
Instead of using infinite pressure for simplification of equation 1, the condition
of zero pressure is used. At p = 0 an exact relationship between the
compacity and o can be derived. By substitution the simplified equation q(o)
is obtained, and equation 1 becomes:
(6)
However, q(o) can only be written explicitly for o = 5.8. Only an
approximation is possible below that threshold. Dahl and Michelsen use a
second order polynomial fitted to the analytical solution for 10 < o < 13 that
can be extrapolated to low alpha:
(7)
Since q(o)is a universal function (for each equationofstate), the
combination of equations 6 and 7 form the MHV2 mixing rule. Excess Gibbs
energies, from any activity coefficient model with parameters optimized at
low pressures, can be used to determine o, if o
i
, b
i
, and b are known. To
compute b, a linear mixing rule is assumed as in the original HuronVidal
mixing rules:
(8)
This equation is equivalent to the assumption of zero excess molar volume.
The MHV2 mixing rule was the first successful predictive mixing rule for
equations of state. This mixing rule uses previously determined activity
coefficient parameters for predictions at high pressures. UNIFAC was chosen
as a default for its predictive character. The Lyngby modified UNIFAC
formulation was chosen for optimum performance (see UNIFAC (Lyngby
68 2 Thermodynamic Property Models
Modified)). However, any activity coefficient model can be used when its
binary interaction parameters are known.
Like the HuronVidal mixing rules, the MHV2 mixing rules are not flexible in
the description of the excess molar volume. The MHV2 mixing rules are
theoretically incorrect at the low pressure limit. But the practical
consequences of this drawback are minimal (see HuronVidal Mixing Rules,
this chapter).
Reference: S. Dahl and M.L. Michelsen, "HighPressure VaporLiquid
Equilibrium with a UNIFACbased Equationofstate," AIChE J., Vol. 36,
(1990), pp. 18291836.
Predictive SoaveRedlichKwongGmehling
Mixing Rules
These mixing rules by Holderbaum and Gmehling (1991) use a relationship
between the excess Helmholtz energy and equationofstate. They do not use
a relationship between equationofstate properties and excess Gibbs energy,
as in the HuronVidal mixing rules. The pressureexplicit expression for the
equationofstate is substituted in the thermodynamic equation:
(1)
The Helmholtz energy is calculated by integration. A
E
is obtained by:
(2)
Where both A
i
* and A
m
are calculated by using equation 1. A
i
* and A
m
are
written in terms of equationofstate parameters.
The simplification of constant packing fraction (V
m
/ b) is used:
(3)
With:
(4)
Therefore:
(5)
The mixing rule is:
(6)
Where A' is slightly different from A for the HuronVidal mixing rule:
2 Thermodynamic Property Models 69
(7)
Where
1
and
2
, depend on the equationofstate (see HuronVidal Mixing
Rules). If equation 6 is applied at infinite pressure, the packing fraction goes
to 1. The excess Helmholtz energy is equal to the excess Gibbs energy. The
HuronVidal mixing rules are recovered.
The goal of these mixing rules is to be able to use binary interaction
parameters for activity coefficient models at any pressure. These parameters
have been optimized at low pressures. UNIFAC is chosen for its predictive
character. Two issues exist: the packing fraction is not equal to one, and the
excess Gibbs and Helmholtz energy are not equal at the low pressure where
the UNIFAC parameters have been derived.
Fischer (1993) determined that boiling point, the average packing fraction for
about 80 different liquids with different chemical natures was 1.1. Adopting
this value, the difference between liquid excess Gibbs energy and liquid
excess Helmholtz energy can be computed as:
(8)
The result is a predictive mixing rule for cubic equations of state. But the
original UNIFAC formulation gives the best performance for any binary pair
with interactions available from UNIFAC. Gassolvent interactions are
unavailable.
At the University of Oldenburg in Germany, the UNIFAC groups were
extended with oftenoccurring gases. New group interactions were
determined from gassolvent data, specific to the RedlichKwongSoave
equationofstate. The new builtin parameters to the Aspen Physical Property
System are activated when using the PSRK equationofstate model.
The PSRK method has a lot in common with the HuronVidal mixing rules. The
mole fraction is dependent on the second virial coefficient and excess volume
is predicted. These are minor disadvantages.
References
K. Fischer, "Die PSRKMethode: Eine Zustandsgleichung unter Verwendung
des UNIFACGruppenbeitragsmodells," (Dsseldorf: VDI Fortschrittberichte,
Reihe 3: Verfahrenstechnik, Nr. 324, VDI Verlag GmbH, 1993).
T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equationof
state based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251265.
70 2 Thermodynamic Property Models
WongSandler Mixing Rules
These mixing rules use a relationship between the excess Helmholtz energy
and equationofstate. They do not use a relationship between equationof
state properties and excess Gibbs energy, as in the HuronVidal mixing rules.
The pressureexplicit expression for the equationofstate is substituted in the
thermodynamic equation:
(1)
The Helmholtz energy is obtained by integration, A
E
is obtained by:
(2)
Where both A
i
* and A
m
are calculated by using equation 1. A
i
* and A
m
are
written in terms of equationofstate parameters.
Like Huron and Vidal, the limiting case of infinite pressure is used. This
simplifies the expressions for A
i
* and A
m
. Equation 2 becomes:
(3)
Where A depends on the equationofstate (see HuronVidal Mixing Rules).
Equation 3 is completely analogous to the HuronVidal mixing rule for the
excess Gibbs energy at infinite pressure. (See equation 4, HuronVidal Mixing
Rules.) The excess Helmholtz energy can be approximated by the excess
Gibbs energy at low pressure from any liquid activity coefficient model. Using
the Helmholtz energy permits another mixing rule for b than the linear mixing
rule. The mixing rule for b is derived as follows. The second virial coefficient
must depend quadratically on the mole fraction:
(4)
With:
(5)
The relationship between the equationofstate at low pressure and the virial
coefficient is:
(6)
(7)
Wong and Sandler discovered the following mixing rule to satisfy equation 4
(using equations 6 and 7):
2 Thermodynamic Property Models 71
The excess Helmholtz energy is almost independent of pressure. It can be
approximated by the Gibbs energy at low pressure. The difference between
the two functions is corrected by fitting k
ij
until the excess Gibbs energy from
the equationofstate (using the mixing rules 3 and 8) is equal to the excess
Gibbs energy computed by an activity coeffecient model. This is done at a
specific mole fraction and temperature.
This mixing rule accurately predicts the VLE of polar mixtures at high
pressures. UNIFAC or other activity coeffecient models and parameters from
the literature are used. Gas solubilities are not predicted. They must be
regressed from experimental data.
Unlike other (modified) HuronVidal mixing rules, the Wong and Sandler
mixing rule meets the theoretical limit at low pressure. The use of k
ij
does
influence excess molar volume behavior. For calculations where densities are
important, check whether they are realistic.
References
D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for
Cubic Equations of State for Both Highly and Slightly Nonideal Mixtures,"
AIChE J., Vol. 38, (1992), pp. 671 680.
D. S. Wong, H. Orbey, and S. I. Sandler, "Equationofstate Mixing Rule for
Nonideal Mixtures Using Available Activity Coefficient Model Parameters and
That Allows Extrapolation over Large Ranges of Temperature and Pressure",
Ind Eng Chem. Res., Vol. 31, (1992), pp. 2033 2039.
H. Orbey, S. I. Sandler and D. S. Wong, "Accurate Equationofstate
Predictions at High Temperatures and Pressures Using the Existing UNIFAC
Model," Fluid Phase Eq., Vol. 85, (1993), pp. 41 54.
Activity Coefficient Models
The Aspen Physical Property System has the following builtin activity
coefficient models. This section describes the activity coefficient models
available.
Model Type
BromleyPitzer Electrolyte
ChienNull Regular solution, local composition
Constant Activity Coefficient Arithmetic
CosmoSAC Regular solution
Electrolyte NRTL Electrolyte
Ideal Liquid Ideal
NRTL (NonRandomTwoLiquid) Local composition
72 2 Thermodynamic Property Models
Model Type
Pitzer Electrolyte
Polynomial Activity Coefficient Arithmetic
RedlichKister Arithmetic
ScatchardHildebrand Regular solution
ThreeSuffix Margules Arithmetic
UNIFAC Group contribution
UNIFAC (Lyngby modified) Group contribution
UNIFAC (Dortmund modified) Group contribution
UNIQUAC Local composition
Van Laar Regular solution
Wagner interaction parameter Arithmetic
Wilson Local composition
Wilson with Liquid Molar Volume Local composition
BromleyPitzer Activity Coefficient Model
The BromleyPitzer activity coefficient model is a simplified Pitzer activity
coefficient model with Bromley correlations for the interaction parameters.
See Working Equations for a detailed description. This model has predictive
capabilities. It can be used to compute activity coefficients for aqueous
electrolytes up to 6 molal ionic strength, but is less accurate than the Pitzer
model if the parameter correlations are used. The model should not be used
for mixedsolvent electrolyte systems.
The BromleyPitzer model in the Aspen Physical Property System involves
usersupplied parameters, used in the calculation of binary parameters for the
electrolyte system.
Parameters 
(0)
, 
(1)
, 
(2)
, 
(3)
, and u have five elements to account for
temperature dependencies. Elements P1 through P5 follow the temperature
dependency relation:
Where:
T
ref
= 298.15K
The user must:
 Supply these elements using a Properties Parameters Binary TDependent
form.
 Specify Comp ID i and Comp ID j on this form, using the same order that
appears on the Components Specifications Selection sheet form.
Parameter Name Symbol No. of ElementsDefault Units
Ionic Unary Parameters
GMBPB

ion
1 0
GMBPD
o
ion
1 0
2 Thermodynamic Property Models 73
Parameter Name Symbol No. of ElementsDefault Units
Ionic Unary Parameters
CationAnion Parameters
GMBPB0

(0)
5 0
GMBPB1

(1)
5 0
GMBPB2

(2)
5 0
GMBPB3

(3)
5 0
CationCation Parameters
GMBPTH
u
cc'
5 0
AnionAnion Parameters
GMBPTH
u
aa'
5 0
MoleculeIon and MoleculeMolecule Parameters
GMBPB0

(0)
5 0
GMBPB1

(1)
5 0
Working Equations
The complete Pitzer equation (Frst and Renon, 1982) for the excess Gibbs
energy is (see also equation 4):
(1)
Where:
G
E
= Excess Gibbs energy
R = Gas constant
T = Temperature
n
w
= Kilograms of water
z
i
= Charge number of ion i
= molality of ion i
Where:
x
i
= Mole fraction of ion i
x
w
= Mole fraction of water
M
w
= Molecular weight of water (g/mol)
n
i
= Moles of ion i
74 2 Thermodynamic Property Models
B, C, u and + are interaction parameters, and f(I) is an electrostatic term as
a function of ionic strength; these terms are discussed in Pitzer Activity
Coefficient Model, which has a detailed discussion of the Pitzer model.
The C term and the + term are dropped from equation 1 to give the
simplified Pitzer equation.
(2)
Where:
B
ij
=
f(
ij
(0)
,
ij
(1)
,
ij
(2)
,
ij
(3)
)
Therefore, the simplified Pitzer equation has two types of binary interaction
parameters,  's and u''s. There are no ternary interaction parameters with
the simplified Pitzer equation.
Note that the Pitzer model parameter databank described in Physical Property
Data, Chapter 1, is not applicable to the simplified Pitzer equation.
A builtin empirical correlation estimates the 
(0)
and 
(1)
parameters for
cationanion pairs from the Bromley ionic parameters, 
ion
and o
ion
(Bromley,
1973). The estimated values of 
(0)
's and 
(1)
's are overridden by the user's
input. For parameter naming and requirements, see BromleyPitzer Activity
Coefficient Model.
References
L.A. Bromley, "Thermodynamic Properties of Strong Electrolytes in Aqueous
Solution, " AIChE J., Vol. 19, No. 2, (1973), pp. 313 320.
W. Frst and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to SolidLiquid Equilibrium. Preliminary Study for Strong 11
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396400.
Parameter Conversion
For nm electrolytes, n and m>1 (22, 23, 34, and so on), the parameter

(3)
corresponds to Pitzer's 
(1)
; 
(2)
is the same in both Aspen Physical
Property System and original Pitzer models. Pitzer refers to the nm
electrolyte parameters as 
(1)
, 
(2)
, 
(0)
. 
(0)
and 
(2)
retain their meanings in
both models, but Pitzer's 
(1)
is Aspen Physical Property System 
(3).
Be
careful to make this distinction when entering nm electrolyte parameters.
ChienNull
The ChienNull model calculates liquid activity coefficients and it can be used
for highly nonideal systems. The generalized expression used in its derivation
2 Thermodynamic Property Models 75
can be adapted to represent other well known formalisms for the activity
coefficient by properly defining its binary terms. This characteristic allows the
model the use of already available binary parameters regressed for those
other liquid activity models with thermodynamic consistency.
The equation for the ChienNull liquid activity coeficient is:
Where:
R
ji
= A
ji
/ A
ij
A
ii
= 0
A
ij
= a
ij
+ b
ij
/ T
Subscripts i and j are component indices.
The choice of model and parameters can be set for each binary pair
constituting the process mixture by assigning the appropriate value to the
ICHNUL parameter.
The Regular Solution and ScatchardHamer models are regained by
substituting in the general expression (ICHNUL = 1 or 2).
V
ji
= S
ji
= V
j
*,l
/ V
i
*,l
Where:
V
j
*,l
= Liquid molar volume of component i
The ChienNull activity coefficient model collapses to the Margules liquid
activity coefficient expression by setting (ICHNUL = 3):
V
ji
= S
ji
= 1
The Van Laar Liquid activity coefficient model is obtained when the V and S
parameters in the ChienNull models are set to the ratio of the cross terms of
A (ICHNUL = 4:)
V
ji
= S
ji
= A
ji
/ A
ij
Finally, the Renon or NRTL model is obtained when we make the following
susbstitutions in the ChienNull expression for the liquid activity (ICHNUL =
5).
S
ji
= R
ji
A
ji
/ A
ij
A
ji
= 2t
ji
G
ji
V
ji
= G
ji
The following are defined for the NonRandom TwoLiquid activity coefficient
model, where:
76 2 Thermodynamic Property Models
t
ij
= a
ij
+ b
ij
/ T
C
ij
= c
ij
+ d
ij
(T  273.15 K)
c
ji
= c
ij
d
ji
= d
ij
The binary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be
determined from regression of VLE and/or LLE data. Also, if you have
parameters for many of the mixture pairs for the Margules, Van Laar,
ScatchardHildebrand, and NRTL (NonRandomTwoLiquid) activity models,
you can use them directly with the ChienNull activity model after selecting
the proper code (ICHNUL) to identify the source model and entering the
appropriate activity model parameters.
Parameter
Name/Element
Symbol Default Lower
Limit
Upper
Limit
Units
ICHNUL 3 1 6
CHNULL/1 a
ij
0
CHNULL/2 b
ij
0
CHNULL/3 V
ij
0
The parameter ICHNUL is used to identify the activity model parameters
available for each binary pair of interest. The following values are allowed for
ICHNUL:
ICHNUL = 1 or 2, sets the model to the ScatchardHamer or regular solution
model for the associated binary;
ICHNUL = 3, sets the model to the ThreeSuffix Margules activity model for
the associated binary;
ICHNUL = 4, sets the model to the Van Laar formalism for the activity model
for the associated binary;
ICHNUL = 5, sets the model to the NRTL (Renon) formalism for the activity
model for the associated binary.
ICHNUL = 6, sets the model to the full ChienNull formalism for the activity
model for the associated binary.
When you specify a value for the ICHNUL parameter that is different than the
default, you must enter the appropriate binary model parameters for the
chosen activity model directly. The routine will automatically convert the
expressions and parameters to conform to the ChienNull formulation.
Constant Activity Coefficient
This approach is used exclusively in metallurgical applications where multiple
liquid and solid phases can coexist. You can assign any value to the activity
coefficient of component i. Use the Properties Parameters Unary Scalar form.
The equation is:
i
= a
i
Parameter
Name/Element
Symbol Default MDS Upper
Limit
Lower
Limit
Units
2 Thermodynamic Property Models 77
Parameter
Name/Element
Symbol Default MDS Upper
Limit
Lower
Limit
Units
GMCONS a
i
1.0 x
COSMOSAC
CosmoSAC is a solvation model that describes the electric fields on the
molecular surface of species that are polarizable. It requires a fairly
complicated quantum mechanical calculation, but this calculation must be
done only once for a particular molecule; then the results can be stored. In its
final form, it uses individual atoms as the building blocks for predicting phase
equilibria instead of functional groups. This model formulation provides a
considerably larger range of applicability than groupcontribution methods.
The calculation for liquid nonideality is only slightly more computationally
intensive than activitycoefficient models such as NRTL or UNIQUAC. Cosmo
SAC complements the UNIFAC groupcontribution method, because it is
applicable to virtually any mixture.
The CosmoSAC model calculates liquid activity coefficients. The equation for
the CosmoSAC model is:
With
78 2 Thermodynamic Property Models
Where:
i
=Activity coefficient of component i
i
SG
=StavermanGuggenheim model for combinatorial
contribution to
i
I
i
(o
m
)
=
Segment activity coefficient of segment o
m
in
component i
I
S
(o
m
)
=
Segment activity coefficient of segment o
m
in
solvent mixture
p
i
(o
m
)
=Sigma profile of component i
p
i
(o
m
)
=Sigma profile of solvent mixture
o
=Surface charge density
AW(o
m
,o
n
)
=
Exchange energy between segments o
m
and o
n
AW
HB
(o
m
,o
n
)
=Hydrogenbonding contribution to exchange energy
between segments o
m
and o
n
z =Coordination number, 10
V
i
=Molecular volume of component i
A
i
=Molecular surface area of component i
a
eff
=Standard segment surface area, 7.50
2
V
eff
=Standard component volume, 66.69
3
A
eff
=Standard component surface area, 79.53
2
o'
=Misfit energy constant
The CosmoSAC model does not require binary parameters. For each
component, it has six input parameters. CSACVL is the component volume
parameter which is always defined in cubic angstroms, regardless of chosen
2 Thermodynamic Property Models 79
units sets. SGPRF1 to SGPRF5 are five component sigma profile parameters;
each can store up to 12 points of sigma profile values. All six input
parameters are obtained from COSMO calculation. The Aspen Physical
Property System includes a database of sigma profiles for over 1400
compounds from Mullins et al. (2006). The parameters were obtained by
permission from the Virginia Tech Sigma Profile Database website
(http://www.design.che.vt.edu/VT2004.htm). Aspen Technology, Inc. does
not claim proprietary rights to these parameters.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CSACVL V
i
x VOLUME (
3
)
SGPRF1 A
i
p
i
(112) x
SGPRF2 A
i
p
i
(1324) x
SGPRF3 A
i
p
i
(2536) x
SGPRF4 A
i
p
i
(3748) x
SGPRF5 A
i
p
i
(4951) x
Option Codes
The primary version of COSMOSAC is the model by Lin and Sandler (2002).
Two other versions are available using an option code, as detailed in the table
below:
Option
Code
Description
1 COSMOSAC model by Lin and Sandler (2002)
2 COSMORS model by Klamt and Eckert (2000)
3 Lin and Sandler model with modified exchange energy (Lin
et al., 2002)
References
A. Klamt and F. Eckert, "COSMORS: A Novel and Efficient Method for the a
Priori Prediction of Thermophysical Data of Liquids," Fluid Phase Equilibria 43,
172 (2000).
S.T. Lin, P. M. Mathias, Y. Song, C.C. Chen, and S. I. Sandler,
"Improvements of PhaseEquilibrium Predictions for HydrogenBonding
Systems from a New Expression for COSMO Solvation Models," presented at
the AIChE Annual Meeting, Indianapolis, IN, 38 November (2002).
S.T. Lin and S. I. Sandler, "A Priori Phase Equilibrium Prediction from a
Segment Contribution Solvation Model," Ind. Eng. Chem. Res. 41, 899
(2002).
E. Mullins, et al. "SigmaProfile Database for Using COSMOBased
Thermodynamic Methods," Ind. Eng. Chem. Res. 45, 4389 (2006).
Electrolyte NRTL Activity Coefficient Model
The Electrolyte NonRandom Two Liquid (NRTL) model is a versatile model for
the calculation of activity coefficients. Using binary and pair parameters, the
model can represent aqueous electrolyte systems as well as mixed solvent
80 2 Thermodynamic Property Models
electrolyte systems over the entire range of electrolyte concentrations. This
model can calculate activity coefficents for ionic species and molecular species
in aqueous electrolyte systems as well as in mixed solvent electrolyte
systems. The model reduces to the wellknown NRTL model when electrolyte
concentrations become zero (Renon and Prausnitz, 1969).
The electrolyte NRTL model uses the infinite dilution aqueous solution as the
reference state for ions. It adopts the Born equation to account for the
transformation of the reference state of ions from the infinite dilution mixed
solvent solution to the infinite dilution aqueous solution.
Water must be present in the electrolyte system in order to compute the
transformation of the reference state of ions. Thus, it is necessary to
introduce a trace amount of water to use the model for nonaqueous
electrolyte systems.
The Aspen Physical Property System uses the electrolyte NRTL model to
calculate activity coefficients, enthalpies, and Gibbs energies for electrolyte
systems. Model development and working equations are provided in
Theoretical Basis and Working Equations.
The adjustable parameters for the electrolyte NRTL model include the:
 Pure component dielectric constant coefficient of nonaqueous solvents
 Born radius of ionic species
 NRTL parameters for moleculemolecule, moleculeelectrolyte, and
electrolyteelectrolyte pairs
The pure component dielectric constant coefficients of nonaqueous solvents
and Born radius of ionic species are required only for mixedsolvent
electrolyte systems. The temperature dependency of the dielectric constant of
solvent B is:
Each type of electrolyte NRTL parameter consists of both the nonrandomness
factor, o, and energy parameters, t. The temperature dependency relations
of the electrolyte NRTL parameters are:
 MoleculeMolecule Binary Parameters:
 ElectrolyteMolecule Pair Parameters:
 ElectrolyteElectrolyte Pair Parameters:
2 Thermodynamic Property Models 81
For the electrolyteelectrolyte pair parameters, the two electrolytes must
share either one common cation or one common anion:
Where:
T
ref
= 298.15K
Many parameter pairs are included in the electrolyte NRTL model parameter
databank (see Physical Property Data, Chapter 1).
Certain Electrolyte NRTL activity coefficient model parameters are used with
reciprocal temperature terms:
 CPDIEC
 NRTL/2
 GMELCD for electrolyteelectrolyte or electrolytemolecule pairs
When any of these parameters is specified, absolute temperature units are
used for the calculations in this model.
Option codes can affect the performance of this model. See Option Codes for
Activity Coefficient Models for details.
Parameter
Name
Symbol No. of
Elements
Default MDS Units
Dielectric Constant Unary Parameters
CPDIEC A
B
1
B
B
1 0
C
B
1 298.15 TEMPERATURE
B
B'B
0 x TEMPERATURE
NRTL/3
o
BB'
= o
B'B
.3 x
NRTL/4 0 x TEMPERATURE
NRTL/5 F
BB'
0 x TEMPERATURE
F
B'B
0 x TEMPERATURE
NRTL/6 G
BB'
0 x TEMPERATURE
G
B'B
0 x TEMPERATURE
ElectrolyteMolecule Pair Parameters
GMELCC C
ca,B
1 0 x
C
B,ca
1 0 x
GMELCD D
ca,B
1 0 x TEMPERATURE
GMELCE E
ca,B
1 0 x
E
B,ca
1 0 x
GMELCN
o
ca,B
= o
B,ca
1 .2 x
ElectrolyteElectrolyte Pair Parameters
GMELCC C
ca',ca''
1 0 x
C
ca'',ca'
1 0 x
C
c'a,c''a
1 0 x
C
c''a,c'a
1 0 x
GMELCD D
ca',ca''
1 0 x TEMPERATURE
D
ca'',ca'
1 0 x TEMPERATURE
D
c'a,c''a
1 0 x TEMPERATURE
D
c''a,c'a
1 0 x TEMPERATURE
GMELCE E
ca',ca''
1 0 x
E
ca'',ca'
1 0 x
E
c'a,c''a
1 0 x
E
c''a,c'a
1 0 x
GMELCN
o
ca',ca''
= o
ca'',ca'
1 .2 x
o
c'a,c''a
= o
c''a,c'a
1 .2 x
Certain Electrolyte NRTL activity coefficient model parameters are used with
reciprocal temperature terms:
 CPDIEC
 NRTL/2
 GMELCD for electrolyteelectrolyte or electrolytemolecule pairs
When any of these parameters is specified, absolute temperature units are
used for the calculations in this model.
Reference: H. Renon, and J.M. Prausnitz, "Local Compositions in
Thermodynamic Excess Functions for Liquid Mixtures", AIChE J., Vol. 14, No.
1, (1968), pp. 135144.
Theoretical Basis and Working Equations
In this section, the theoretical basis of the model is explained and the working
equations are given. The different ways parameters can be obtained are
discussed with references to the databank directories and the Data
Regression System (DRS). The parameter requirements of the model are
given in Electrolyte NRTL Activity Coefficient Model.
2 Thermodynamic Property Models 83
Development of the Model
The Electrolyte NRTL model was originally proposed by Chen et al., for
aqueous electrolyte systems. It was later extended to mixed solvent
electrolyte systems (Mock et al., 1984, 1986). The model is based on two
fundamental assumptions:
 The likeion repulsion assumption: states that the local composition of
cations around cations is zero (and likewise for anions around anions).
This is based on the assumption that the repulsive forces between ions of
like charge are extremely large. This assumption may be justified on the
basis that repulsive forces between ions of the same sign are very strong
for neighboring species. For example, in salt crystal lattices the immediate
neighbors of any central ion are always ions of opposite charge.
 The local electroneutrality assumption: states that the distribution of
cations and anions around a central molecular species is such that the net
local ionic charge is zero. Local electroneutrality has been observed for
interstitial molecules in salt crystals.
Chen proposed an excess Gibbs energy expression which contains two
contributions: one contribution for the longrange ionion interactions that
exist beyond the immediate neighborhood of a central ionic species, and the
other related to the local interactions that exist at the immediate
neighborhood of any central species.
The unsymmetric PitzerDebyeHckel model and the Born equation are used
to represent the contribution of the longrange ionion interactions, and the
NonRandom Two Liquid (NRTL) theory is used to represent the local
interactions. The local interaction contribution model is developed as a
symmetric model, based on reference states of pure solvent and pure
completely dissociated liquid electrolyte. The model is then normalized by
infinite dilution activity coefficients in order to obtain an unsymmetric model.
This NRTL expression for the local interactions, the PitzerDebyeHckel
expression, and the Born equation are added to give equation 1 for the
excess Gibbs energy (see the following note).
(1)
This leads to
(2)
Note: The notation using * to denote an unsymmetric reference state is well
accepted in electrolyte thermodynamics and will be maintained here. The
reader should be warned not to confuse it with the meaning of * in classical
thermodynamics according to IUPAC/ISO, referring to a pure component
property. In fact in the context of G or , the asterisk as superscript is never
used to denote pure component property, so the risk of confusion is minimal.
For details on notation, see Chapter 1 of Physical Property Methods.
References
C.C. Chen, H.I. Britt, J.F. Boston, and L.B. Evans, "Local Compositions Model
for Excess Gibbs Energy of Electrolyte Systems: Part I: Single Solvent, Single
84 2 Thermodynamic Property Models
Completely Dissociated Electrolyte Systems:, AIChE J., Vol. 28, No. 4, (1982),
p. 588596.
C.C. Chen, and L.B. Evans, "A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems," AIChE J., Vol. 32, No. 3, (1986), p.
444459.
B. Mock, L.B. Evans, and C.C. Chen, "Phase Equilibria in MultipleSolvent
Electrolyte Systems: A New Thermodynamic Model," Proceedings of the 1984
Summer Computer Simulation Conference, p. 558.
B. Mock, L.B. Evans, and C.C. Chen, "Thermodynamic Representation of
Phase Equilibria of MixedSolvent Electrolyte Systems," AIChE J., Vol. 32, No.
10, (1986), p. 16551664.
LongRange Interaction Contribution
The PitzerDebyeHckel formula, normalized to mole fractions of unity for
solvent and zero for electrolytes, is used to represent the longrange
interaction contribution.
(3)
Where:
x
k
= Mole fraction of component k
M
B
= Molecular weight of the solvent B
A
= DebyeHckel parameter:
A
= (4)
N
A
= Avogadro's number
d = Density of solvent
Q
e
= Electron charge
c
w
= Dielectric constant of water
T = Temperature
k = Boltzmann constant
I
x
= Ionic strength (mole fraction scale):
I
x
= (5)
x
i
= Mole fraction of component i
z
i
= Charge number of ion i
I
*
= Unsymmetric activity coefficient of an ionic species I
I
*lc
= NRTL term
2 Thermodynamic Property Models 95
I
*PDH
= PitzerDebyeHckel term
I
*FH
= FloryHuggins term
= Aqueousphase infinitedilution reference state
I
i
= Activity coefficient of conceptual segment i
r
I
= Total segment number of component I
x
I
= Mole fraction of component I
r
I,i
= Number of conceptual segment i containing in component I
x
i
= Segment mole fraction of conceptual segment i in mixtures
o
ij
= NRTL binary nonrandomness factor parameter for
conceptual segments
t
ij
= NRTL binary interaction energy parameter for conceptual
segments
A
= DebyeHckel parameter
i
= Activity coefficient of component i
V
i
= Molar volume of component i
o
i
d
= Hansen solubility parameter of component i for nonpolar
effect
o
i
p
= Hansen solubility parameter of component i for polar effect
o
i
h
= Hansen solubility parameter of component i for hydrogen
bonding effect

i
= Volume fraction of component i
x
i
= Mole fraction of component i
R = Gas constant
T = Temperature
The Hansen model does not require binary parameters. For each component,
it has four input parameters.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DELTAD
o
i
d
x PRESSURE^0.5
DELTAP
o
i
p
x PRESSURE^0.5
DELTAH
o
i
h
x PRESSURE^0.5
HANVOL V
i
x VOLUME
Option codes
The Hansen volume is implemented as an input parameter. If the Hansen
volume is not input by the user it will be calculated by an Aspen Plus internal
method. You can also request the Aspen Plus method using Option Codes in
Aspen Plus Interface. The table below lists the option codes.
98 2 Thermodynamic Property Models
First Option Code in Hansen model
0 Hansen volume input by user (default)
Other values Hansen volume calculated by Aspen Plus
Reference
Frank, T. C.; Downey, J. R.; Gupta, S. K. "Quickly Screen Solvents for
Organic Solids," Chemical Engineering Progress 1999, December, 41.
Hansen, C. M. Hansen Solubility Parameters: A Users Handbook; CRC Press,
2000.
Ideal Liquid
This model is used in Raoult's law. It represents ideality of the liquid phase.
This model can be used for mixtures of hydrocarbons of similar carbon
number. It can be used as a reference to compare the results of other activity
coefficient models.
The equation is:
ln
i
= 0
NRTL (NonRandom TwoLiquid)
The NRTL model calculates liquid activity coefficients for the following
property methods: NRTL, NRTL2, NRTLHOC, NRTLNTH, and NRTLRK. It is
recommended for highly nonideal chemical systems, and can be used for VLE
and LLE applications. The model can also be used in the advanced equation
ofstate mixing rules, such as WongSandler and MHV2.
The equation for the NRTL model is:
Where:
G
ij
=
t
ij
=
o
ij
=
t
ii
= 0
G
ii
= 1
a
ij
, b
ij
, c
ij
, and f
ij
are unsymmetrical. That is, a
ij
may not be equal to a
ji
, etc.
2 Thermodynamic Property Models 99
Recommended c
ij
Values for Different Types of Mixtures
c
ij
Mixtures
0.30 Nonpolar substances; nonpolar with polar nonassociated liquids; small
deviations from ideality
0.20 Saturated hydrocarbons with polar nonassociated liquids and systems that
exhibit liquidliquid immiscibility
0.47 Strongly selfassociated substances with nonpolar substances
The binary parameters a
ij
, b
ij
, c
ij
, d
ij
, e
ij
, and f
ij
can be determined from VLE
and/or LLE data regression. The Aspen Physical Property System has a large
number of builtin binary parameters for the NRTL model. The binary
parameters have been regressed using VLE and LLE data from the Dortmund
Databank. The binary parameters for the VLE applications were regressed
using the ideal gas, RedlichKwong, and Hayden O'Connell equations of state.
See Physical Property Data, Chapter 1, for details.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
NRTL/1 a
ij
0 x 100.0 100.0
NRTL/2 b
ij
0 x 30000 30000.0 TEMPERATURE
NRTL/3 c
ij
0.30 x 0.0 1.0
NRTL/4 d
ij
0 x 0.02 0.02 TEMPERATURE
NRTL/5 e
ij
0 x TEMPERATURE
NRTL/6 f
ij
0 x TEMPERATURE
The NRTL2 property method uses data set 2 for NRTL. All other NRTL
methods use data set 1.
References
H. Renon and J.M. Prausnitz, "Local Compositions in Thermodynamic Excess
Functions for Liquid Mixtures," AIChE J., Vol. 14, No. 1, (1968), pp. 135
144.
NRTLSAC
NRTLSAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers Plus. NRTLSAC can be used for fast, qualitative estimation of
the solubility of complex organic compounds in common solvents.
Conceptually, the model treats the liquid nonideality of mixtures containing
complex organic molecules (solute) and small molecules (solvent) in terms of
interactions between three pairwise interacting conceptual segments:
hydrophobic segment (x), hydrophilic segment (z), and polar segments (y
and y+). In practice, these conceptual segments become the molecular
descriptors used to represent the molecular surface characteristics of each
solute or solvent molecule. Hexane, water, and acetonitrile are selected as
the reference molecules for the hydrophobic, hydrophilic, and polar segments,
respectively. The molecular parameters for all other solvents can be
determined by regression of available VLE or LLE data for binary systems of
solvent and the reference molecules or their substitutes. The treatment
results in four componentspecific molecular parameters: hydrophobicity X,
100 2 Thermodynamic Property Models
hydrophilicity Z, and polarity Y and Y+. The two types of polar segments, Y
and Y+, are used to reflect the wide variations of interactions between polar
molecules and water.
The conceptual segment contribution approach in NRTLSAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTLSAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTLSAC model calculates liquid activity coefficients. The equation for
the NRTLSAC model is:
with
G = exp(ot)
Where:
2 Thermodynamic Property Models 101
I, J = Component index
i, j, m = Conceptual segment indexx, y, y+, z
I
= Activity coefficient of component I
I
C
=
I
FH
=
FloryHuggins term for combinatorial contribution to
I
I
R
=
I
lc
= NRTL term for local composition interaction contribution to
I

I
= Segment mole fraction of component I
p
I
= Effective component size parameter
s
I
and c
I
= Empirical parameters for p
I
r
I
= Total segment number of component I
x
I
= Mole fraction of component I
r
I,m
= Number of conceptual segment m containing in component
I
x
i
= Segment mole fraction of conceptual segment i in mixtures
o
im
= NRTL binary nonrandomness factor parameter for
conceptual segments
t
im
= NRTL binary interaction energy parameter for conceptual
segments
NRTL binary parameters for conceptual segments
The NRTL binary parameters between conceptual segments in NRTLSAC are
determined by available VLE and LLE data between reference molecules
defined above.
Segment 1 x x y y+ x
Segment 2 y z z z y+
t
12
1.643 6.547 2.000 2.000 1.643
t
21
1.834 10.949 1.787 1.787 1.834
o
12
= o
21
0.2 0.2 0.3 0.3 0.2
Parameters used in NRTLSAC
Each component can have up to four parameters, r
I,x
, r
I,y
, r
I,y+
, and r
I,z
although only one or two of these molecular parameters are needed for most
solvents in practice. Since conceptual segments apply to all molecules, these
four molecular parameters are implemented together as a binary parameter,
NRTLXY(I, m) where I represents a component (molecule) index and m
represents a conceptual segment index.
In addition, the FloryHuggins size parameter, FHSIZE , is used in NRTLSAC
to calculate the effective component size parameter, p
I
. The FloryHuggins
combinatorial term can be turned off by setting c
I
= 0 for each component in
mixtures.
102 2 Thermodynamic Property Models
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units Comment
NRTLXY r
I,m
Binary,
symmetric
FHSIZE/1 s
I
1.0 1E15 1E15 Unary
FHSIZE/2
c
I
1.0 1E10 1E10 Unary
Option codes
The FloryHuggins term is included by default in the NRTLSAC model. You
can remove this term using the first option code. The table below lists the
values for this option code.
0 FloryHuggins term included (default)
Others FloryHuggins term removed
NRTLSAC molecular parameters for common solvents
The molecular parameters are identified for 62 solvents and published.
Solvent name r
I,x
r
I,y
r
I,y+
r
I,z
ACETICACID 0.045 0.164 0.157 0.217
ACETONE 0.131 0.109 0.513
ACETONITRILE 0.018 0.131 0.883
ANISOLE 0.722
BENZENE 0.607 0.190
1BUTANOL 0.414 0.007 0.485
2BUTANOL 0.335 0.082 0.355
NBUTYLACETATE 0.317 0.030 0.330
METHYLTERTBUTYLETHER 1.040 0.219 0.172
CARBONTETRACHLORIDE 0.718 0.141
CHLOROBENZENE 0.710 0.424
CHLOROFORM 0.278 0.039
CUMENE 1.208 0.541
CYCLOHEXANE 0.892
1,2DICHLOROETHANE 0.394 0.691
1,1DICHLOROETHYLENE 0.529 0.208
1,2DICHLOROETHYLENE 0.188 0.832
DICHLOROMETHANE 0.321 1.262
1,2DIMETHOXYETHANE 0.081 0.194 0.858
N,NDIMETHYLACETAMIDE 0.067 0.030 0.157
2 Thermodynamic Property Models 103
Solvent name r
I,x
r
I,y
r
I,y+
r
I,z
N,NDIMETHYLFORMAMIDE 0.073 0.564 0.372
DIMETHYLSULFOXIDE 0.532 2.890
1,4DIOXANE 0.154 0.086 0.401
ETHANOL 0.256 0.081 0.507
2ETHOXYETHANOL 0.071 0.318 0.237
ETHYLACETATE 0.322 0.049 0.421
ETHYLENEGLYCOL 0.141 0.338
DIETHYLETHER 0.448 0.041 0.165
ETHYLFORMATE 0.257 0.280
FORMAMIDE 0.089 0.341 0.252
FORMICACID 0.707 2.470
NHEPTANE 1.340
NHEXANE 1.000
ISOBUTYLACETATE 1.660 0.108
ISOPROPYLACETATE 0.552 0.154 0.498
METHANOL 0.088 0.149 0.027 0.562
2METHOXYETHANOL 0.052 0.043 0.251 0.560
METHYLACETATE 0.236 0.337
3METHYL1BUTANOL 0.419 0.538 0.314
METHYLBUTYLKETONE 0.673 0.224 0.469
METHYLCYCLOHEXANE 1.162 0.251
METHYLETHYLKETONE 0.247 0.036 0.480
METHYLISOBUTYLKETONE 0.673 0.224 0.469
ISOBUTANOL 0.566 0.067 0.485
NMETHYL2PYRROLIDONE 0.197 0.322 0.305
NITROMETHANE 0.025 1.216
NPENTANE 0.898
1PENTANOL 0.474 0.223 0.426 0.248
1PROPANOL 0.375 0.030 0.511
ISOPROPYLALCOHOL 0.351 0.070 0.003 0.353
NPROPYLACETATE 0.514 0.134 0.587
PYRIDINE 0.205 0.135 0.174
SULFOLANE 0.210 0.457
TETRAHYDROFURAN 0.235 0.040 0.320
104 2 Thermodynamic Property Models
Solvent name r
I,x
r
I,y
r
I,y+
r
I,z
1,2,3,4TETRAHYDRONAPHTHALENE0.443 0.555
TOLUENE 0.604 0.304
1,1,1TRICHLOROETHANE 0.548 0.287
TRICHLOROETHYLENE 0.426 0.285
MXYLENE 0.758 0.021 0.316
WATER 1.000
TRIETHYLAMINE 0.557 0.105
1OCTANOL 0.766 0.032 0.624 0.335
Reference
C.C. Chen and Y. Song, "Solubility Modeling with a Nonrandom TwoLiquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).
Using NRTLSAC
NRTLSAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers Plus. NRTLSAC can be used for fast, qualitative estimation of
the solubility of complex organic compounds in common solvents. For more
information about the model, see NRTLSAC.
The NRTLSAC model in the Aspen Physical Property System is a liquid
activity coefficient model called NRTLSAC. To specify it:
1. On the Properties  Specifications sheet, specify an activity coefficient
model, such as NRTL.
2. Click the Properties  Property Methods folder.
3. In the Object Manager, click New.
4. In the Create New ID dialog box, enter a name for the NRTLSAC
method, such as NRTLSAC.
5. In the Base Property Method field, select NRTL.
6. Click the Models tab.
7. Change the Model Name for GAMMA from GMRENON to NRTLSAC.
In order to use NRTLSAC, all components must be defined as oligomers. Four
conceptual segments also must be defined. On the Components  Polymers
 Oligomers sheet, enter a number for at least one conceptual segment for
each oligomer component, as required by the definition of an oligomer. These
numbers are not used by NRTLSAC.
On the Properties  Parameters  Binary Interaction  NRTL1 form,
enter the binary parameters between conceptual segments. In the following
example, the conceptual segments are named X, Y, Y+, and Z.
Segment 1 X X Y Y+ X
Segment 2 Y Z Z Z Y+
AIJ 1.643 6.547 2.000 2.000 1.643
2 Thermodynamic Property Models 105
Segment 1 X X Y Y+ X
Segment 2 Y Z Z Z Y+
AJI 1.834 10.949 1.787 1.787 1.834
CIJ 0.2 0.2 0.3 0.3 0.2
On the Properties  Parameters  Binary Interaction  NRTLXY1 form,
enter a nonzero value for at least one of the four parameters for each
component.
Pitzer Activity Coefficient Model
The Pitzer model was developed as an improvement upon an earlier model
proposed by Guggenheim (1935, 1955). The earlier model worked well at low
electrolyte concentrations, but contained discrepancies at higher
concentrations (>0.1M). The Pitzer model resolved these discrepancies,
without resorting to excessive arrays of higherorder terms.
The model can be used for aqueous electrolyte systems, up to 6 molal ionic
strength. It cannot be used for systems with any other solvent or mixed
solvents.
This section provides theoretical background for the model. All model
equations and parameter requirements are included.
The Pitzer model is commonly used in the calculation of activity coefficients
for aqueous electrolytes up to 6 molal ionic strength. Do not use this model if
a nonaqueous solvent exists. Henry's law parameters are required for all
other components in the aqueous solution. The model development and
working equations are provided in the following sections. Parameter
conversion between the Pitzer notation and our notation is also provided.
The Pitzer model in the Aspen Physical Property System involves user
supplied parameters that are used in the calculation of binary and ternary
parameters for the electrolyte system.
Five elements (P
1
through P
5
) account for the temperature dependencies of
parameters 
(0)
, 
(1)
, 
(2)
, 
(3)
, C
5 0 x
CationCation Parameters
GMPTTH
u
cc'
5 0 x
AnionAnion Parameters
GMPTTH
u
aa'
5 0 x
Ternary Parameters
GMPTPS,
GMPTP1,
GMPTP2,
GMPTP3,
GMPTP4
+
ijk
1 (in each
parameter)
0 x
MoleculeIon and MoleculeMolecule Parameters
GMPTB0

(0)
5 0 x
GMPTB1

(1)
5 0 x
GMPTC
C
5 0 x
Model Development
The Pitzer model analyzes "hardcore" effects in the DebyeHckel theory. It
uses the following expansion as a radial distribution function:
(1)
Where:
g
ij
= Distribution function
r = Radius
q
ij
=
(pair potential of mean force)
With:
z
i
= Charge of ion i
Q
e
= Electron charge
2 Thermodynamic Property Models 107
+
j
(r)
= Average electric potential for ion j
k = Boltzmann's constant
T = Temperature
This radial distribution function is used in the socalled pressure equation that
relates this function and the intermolecular potential to thermodynamic
properties. From this relation you can obtain an expression for the osmotic
coefficient.
Pitzer proposes a general equation for the excess Gibbs energy. The basic
equation is:
(2)
Where:
G
E
= Excess Gibbs energy
R = Gas constant
T = Temperature
n
w
= Kilograms of water
m
i
=
(molality of ion i)
With:
x
i
= Mole fraction of ion i
x
w
= Mole fraction of water
M
w
= Molecular weight of water (g/mol)
n
i
= Moles of ion i
The function f(I) is an electrostatic term that expresses the effect of long
range electrostatic forces between ions. This takes into account the hardcore
effects of the DebyeHckel theory. This term is discussed in detail in the
following section. The parameters
ij
are second virial coefficients that
account for the shortrange forces between solutes i and j. The parameters
ijk
account for the interactions between solutes, i, j, k. For ionion
interactions,
ij
is a function of ionic strength. For moleculeion or molecule
molecule interactions this ionic strength dependency is neglected. The
dependence of
ijk
on ionic strength is always neglected. The matrices
ij
and
ijk
are also taken to be symmetric (that is,
ij
=
ji
).
Pitzer modified this expression for the Gibbs energy by identifying
combinations of functions. He developed interaction parameters that can be
evaluated using experimental data. He selected mathematical expressions for
these parameters that best fit experimental data.
108 2 Thermodynamic Property Models
Pitzer's model can be applied to aqueous systems of strong electrolytes and
to aqueous systems of weak electrolytes with molecular solutes. These
applications are discussed in the following section.
In the Aspen Physical Property System, this model is applied using the
reference state of infinite dilution solution in water for nonwater molecular
solutes and ionic species. The properties such as DHAQFM are obtained at 25
C and 1 atm.
Application of the Pitzer Model to Aqueous Strong
Electrolyte Systems
Pitzer modified his basic equation to make it more useful for data correlation
of aqueous strong electrolytes. He defined a set of more directly observable
parameters to represent combinations of the second and third virial
coefficients. The modified Pitzer equation is:
(3)
z
i
= Charge of ion i
Subscripts c, c', and a, a' denote cations and anions of the solution. B, C, u,
and + are interaction parameters. f(I) is an electrostatic term as a function of
ionic strength. The cationanion parameters B and C are characteristic for an
aqueous singleelectrolyte system. These parameters can be determined by
the properties of pure (apparent) electrolytes. B is expressed as a function of

(0)
and 
(1)
, or of 
(0)
, 
(2)
, and 
(3)
(see equations 11 through 15).
The parameters u and + are for the difference of interaction of unlike ions of
the same sign from the mean of like ions. These parameters can be measured
from commonion mixtures. Examples are NaCl + KCl + H
2
O or NaCl + NaNO
3
+ H
2
O (sic, Pitzer, 1989). These terms are discussed in detail later in this
section.
Frst and Renon (1982) propose the following expression as the Pitzer
equation for the excess Gibbs energy:
(4)
2 Thermodynamic Property Models 109
The difference between equations 3 and 4 is that Pitzer orders cation before
anions. Frst and Renon do not. All summations are taken over all ions i and j
(both cations and anions). This involves making the parameter matrices B
ij
,
C
ij
, u
ij
, and +
ijk
symmetric, as follows:
Secondorder parameters are written B
ij
if i and j are ions of different sign. B
ij
= 0 if the sign of z
i
= sign of z
j
, and B
ii
= 0. Since cations are not ordered
before anions, B
ij
= B
ji
. This eliminates the 2 in the second term in brackets in
Pitzer's original expression (equation 3). Secondorder parameters are written
u
ij
if i and j are ions of the same sign. Thus u
ij
= 0 if the sign of z
i
is different
from the sign of z
j
, and u
ii
= 0 with u
ij
= u
ji
.
Thirdorder parameters are written C
ij
if i and j are ions with different signs.
C
ij
= 0 if the sign of z
i
= sign of z
j
, and C
ii
= 0 with C
ij
= C
ji
. The factor of 2 in
the fifth bracketed term in Pitzer's original expression (equation 3) becomes
1/2 in equation 4. The matrix C is symmetric and is extended to all
ions to make the equation symmetric.
+
ijk
is written for three different ions +
ijk
= +
kij
= +
jki
, and +
ikk
= 0. +
ijk
= 0
if the sign of z
i
=sign of z
j
=sign of z
k
. The factor of 1/6 is different from 1/2
in the last term in brackets in Pitzer's original expression. Pitzer distinguishes
between cations and anions. In Pitzer's original model this parameter appears
twice, as +
cc'a
and +
c'ca
. In this modified model, it appears six times, as +
cc'a
;
+
c'ca
; +
acc'
; +
ac'c
; +
cac'
; and +
c'ac
. Frst and Renon's expression, equation 4,
calculates the expressions for activity coefficients and osmotic coefficients.
Pitzer (1975) modified his model by adding the electrostatic unsymmetrical
mixing effects, producing this modified Pitzer equation for the excess Gibbs
energy:
(4a)
Calculation of Activity Coefficients
The natural logarithm of the activity coefficient for ions is calculated from
equation 4a to give:
110 2 Thermodynamic Property Models
(5)
Where u is neglected and u
ij
and u
'
ij
are the electrostatic unsymmetric mixing
effects:
The X parameters are calculated differently on the option code.
For option code = 1, there is no unsymmetric mixing correction term:
For option code = 0 (default), the unsymmetric mixing correction term is in
polynomial form:
For option code = 1, the unsymmetric mixing correction term is in integral
form:
2 Thermodynamic Property Models 111
For water the logarithm of the activity coefficient is calculated similarly, as
follows:
Applying:
to equation 3 and using:
Where N
w
= moles water, gives:
(6)
f(I), the electrostatic term, is expressed as a function of ionic strength I :
(7)
I, the ionic strength, is defined as:
(8)
Taking the derivative of equation 7 with respect to I, gives:
(9)
So that:
(10)
This equation is used in equation 6. In equations 7 and 9, is the usual Debye
Hckel constant for the osmotic coefficient, determined from:
112 2 Thermodynamic Property Models
(11)
Where:
N
A
= Avogadro's constant
d
w
= Water density
c
B
= Dielectric constant of solvent B
b is an adjustable parameter, which has been optimized in this model to equal
1.2.
B and B' need expressions so that equations 5 and 6 can completely be solved
for the activity coefficients. The parameter B is determined differently for
different electrolyte pairings. For 1n electrolytes (11, 12, 21, and so on)
the following expression gives the parameter B:
(12)
with o
1
=2.0.
For nm electrolytes, n and m>1 (22, 23, 34, and so on), B is determined
by the following expression:
(13)
with o
2
= 12.0 and o
3
= 1.4.
By taking appropriate derivatives, expressions for B' can be derived for 1n
electrolytes:
(14)
and for nm electrolytes:
(15)
The parameters 
(0)
, 
(1)
, 
(2)
, 
(3)
and also C, u, and + can be found in
Pitzer's articles .
After the activity coefficients are calculated, they can be converted to the
mole fraction scale from the molality scale by the following relations:
For solutes:
2 Thermodynamic Property Models 113
(16)
For water as a solvent:
(17)
Where:
m
= Activity coefficient (molality scale)
x
= Activity coefficient (mole fraction scale)
Application of the Pitzer Model to Aqueous
Electrolyte Systems with Molecular Solutes
In aqueous weak electrolyte systems with molecular solutes, the second and
third virial coefficients in the basic Pitzer equation for moleculeion and
moleculemolecule interactions must be considered. The following extensions
of Pitzer's interaction parameters are made.
The secondorder parameters B
ij
are extended to include moleculemolecule
and moleculeion interaction parameters.
The thirdorder parameters +
ijk
are extended to moleculemoleculemolecule
interactions. The following expressions relate +
ijk
to Pitzer's original
ijk
:
+
iii
= 6
iii
However, moleculemolecule interactions were not taken into account by
Pitzer and coworkers. So
iii
is an artificially introduced quantity.
The equations for activity coefficients and the Gibbs free energy are the same
as equations 3 through 6.
Parameters
The Pitzer model in the Aspen Physical Property System involves user
supplied parameters. These parameters are used in the calculation of binary
and ternary parameters for the electrolyte system. These parameters include
the cationanion parameters 
(0)
, 
(1)
, 
(2)
, 
(3)
and C
, cationcation
parameter u
cc'
, anionanion parameter u
aa'
, cation1cation2common anion
parameter +
cc'a
, anion1anion2common cation parameter +
caa'
, and the
moleculeion and moleculemolecule parameters 
(0)
, 
(1)
, and, C
. The
114 2 Thermodynamic Property Models
parameter names in the Aspen Physical Property System and their
requirements are discussed in Pitzer Activity Coefficient Model.
Parameter Conversion
For nm electrolytes, n and m>1 (22, 23, 34, and so on), the parameter

(3)
corresponds to Pitzer's 
(1)
. 
(2)
is the same in both the Aspen Physical
Property System and original Pitzer models. Pitzer refers to the nm
electrolyte parameters as 
(1)
, 
(2)
, 
(0)
. 
(0)
and 
(2)
retain their meanings in
both models, but Pitzer's 
(1)
is 
(3)
in the Aspen Physical Property System. Be
careful to make this distinction when entering nm electrolyte parameters.
Pitzer often gives values of 
(0)
, 
(1)
, 
(2)
, 
(3)
, and C
) for 13
dilute aqueous electrolytes
(Pitzer and Mayorga, 1973) Binary parameters for 11 inorganic
electrolytes, salts of carboxylic acids (11),
tetraalkylammonium halids, sulfonic acids
and salts, additional 11 organic salts, 21
inorganic compounds, 21 organic
electrolytes, 31 electrolytes, 41 and 51
electrolytes
(Pitzer and Mayorga, 1974) Binary parameters for 22 electrolytes in
water at 25C
(Pitzer and Kim, 1974) Binary and ternary parameters for mixed
electrolytes, binary mixtures without a
common ion, mixed electrolytes with three
or more solutes
(Pitzer, 1975) Ternary parameters for systems mixing
doubly and singly charged ions
(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer
solutions
(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties
for sulfuric acid
(Silvester and Pitzer, 1977) Data for NaCl and aqueous NaCl solutions
(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and
perchlorates
(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including
mixtures of sodium carbonate, bicarbonate,
and chloride
(Phutela and Pitzer, 1983) Aqueous calcium chloride
(Conceicao, de Lima, and Pitzer, 1983) Saturated aqueous solutions, including
mixtures of sodium chloride, potassium
chloride, and cesium chloride
(Pabalan and Pitzer, 1987) Parameters for polynomial unsymmetric
mixing term
(Kim and Frederick, 1988) Parameters for integral unsymmetric mixing
term
Pitzer References
Conceicao, M., P. de Lima, and K.S. Pitzer, "Thermodynamics of Saturated
Aqueous Solutions Including Mixtures of NaCl, KCl, and CsCl, "J. Solution
Chem, Vol. 12, No. 3, (1983), pp. 171185.
Frst, W. and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to SolidLiquid Equilibrium. Preliminary Study for Strong 11
116 2 Thermodynamic Property Models
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396400.
Guggenheim, E.A., Phil. Mag., Vol. 7, No. 19, (1935), p. 588.
Guggenheim, E.A. and J.C. Turgeon, Trans. Faraday Soc., Vol. 51, (1955), p.
747.
Kim, H. and W.J. Frederick, "Evaluation of Pitzer Ion Interaction Parameters
of Aqueous Mixed Electrolyte Solution at 25C, Part 2: Ternary Mixing
Parameters," J. Chem. Eng. Data, 33, (1988), pp. 278283.
Pabalan, R.T. and K.S. Pitzer, "Thermodynamics of Concentrated Electrolyte
Mixtures and the Prediction of Mineral Solubilities to High Temperatures for
Mixtures in the system NaKMgClSO4OHH2O," Geochimica Acta, 51,
(1987), pp. 24292443.
Peiper, J.C. and K.S. Pitzer, "Thermodynamics of Aqueous Carbonate
Solutions Including Mixtures of Sodium Carbonate, Bicarbonate, and
Chloride," J. Chem. Thermodynamics, Vol. 14, (1982), pp. 613638.
Phutela, R.C. and K.S. Pitzer, "Thermodynamics of Aqueous Calcium
Chloride," J. Solution Chem., Vol. 12, No. 3, (1983), pp. 201207.
Pitzer, K.S., "Thermodynamics of Electrolytes. I. Theoretical Basis and
General Equations, " J. Phys. Chem., Vol. 77, No. 2, (1973), pp. 268277.
Pitzer, K.S., J. Solution Chem., Vol. 4, (1975), p. 249.
Pitzer, K.S., "Fluids, Both Ionic and NonIonic, over Wide Ranges of
Temperature and Composition," J. Chen. Thermodynamics, Vol. 21, (1989),
pp. 117. (Seventh Rossini lecture of the commission on Thermodynamics of
the IUPAC, Aug. 29, 1988, Prague, exCzechoslovakia).
Pitzer, K.S. and J.J. Kim, "Thermodynamics of Electrolytes IV; Activity and
Osmotic Coefficients for Mixed Electrolytes," J.Am. Chem. Soc., Vol. 96
(1974), p. 5701.
Pitzer, K.S. and G. Mayorga, "Thermodynamics of Electrolytes II; Activity and
Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent,"
J. Phys. Chem., Vol. 77, No. 19, (1973), pp. 23002308.
Pitzer, K.S. and G. Mayorga, J. Solution Chem., Vol. 3, (1974), p. 539.
Pitzer, K.S., J.R. Peterson, and L.F. Silvester, "Thermodynamics of
Electrolytes. IX. Rare Earth Chlorides, Nitrates, and Perchlorates, "J. Solution
Chem., Vol. 7, No. 1, (1978), pp. 4556.
Pitzer, K.S., R.N. Roy, and L.F. Silvester, "Thermodynamics of Electrolytes 7
Sulfuric Acid," J. Am. Chem. Soc., Vol. 99, No. 15, (1977), pp. 49304936.
Pitzer, K.S. and L.F. Silvester, J. Solution Chem., Vol. 5, (1976), p. 269.
Silvester, L.F. and K.S. Pitzer, "Thermodynamics of Electrolytes 8 High
Temperature Properties, Including Enthalpy and Heat Capacity, With
Application to Sodium Chloride," J. Phys. Chem., Vol. 81, No. 19, (1977), pp.
18221828.
2 Thermodynamic Property Models 117
Polynomial Activity Coefficient
This model represents activity coefficient as an empirical function of
composition and temperature. It is used frequently in metallurgical
applications where multiple liquid and solid solution phases can exist.
The equation is:
Where:
A
i
=
B
i
=
C
i
=
D
i
=
E
i
=
For any component i, the value of the activity coefficient can be fixed:
i
= f
i
This model is not part of any property method. To use it:
1. On the Properties  Specifications sheet, specify an activity coefficient
model, such as NRTL.
2. Click the Properties  Property Methods folder.
3. In the Object Manager, click New.
4. In the Create New ID dialog box, enter a name for the new method.
5. In the Base Property Method field, select NRTL.
6. Click the Models tab.
7. Change the Model Name for GAMMA from GMRENON to GMPOLY.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMPLYP/1 a
i1
0 x
GMPLYP/2 a
i2
0 x
GMPLYP/3 a
i3
0 x
GMPLYP/4 b
i1
0 x
GMPLYP/5 b
i2
0 x
GMPLYP/6 b
i3
0 x
GMPLYP/7 c
i1
0 x
GMPLYP/8 c
i2
0 x
GMPLYP/9 c
i3
0 x
GMPLYP/10 d
i1
0 x
GMPLYP/11 d
i2
0 x
GMPLYP/12 d
i3
0 x
GMPLYP/13 e
i1
0 x
GMPLYP/14 e
i2
0 x
118 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMPLYP/15 e
i3
0 x
GMPLYO f
i
x
Note: If you specify GMPLYP on the Properties  Parameters  Pure
Component  TDependent sheet, you can only enter the first 12 elements.
If you want to specify values for elements 13 to 15, you should go to the
Flowsheeting Options  AddInput  Add After sheet in Aspen Plus or the
AddInput  AddInput  Add After sheet in Aspen Properties, and enter
the values of all 15 elements as in the following example:
PROPDATA GMPLYP1
INUNITS SI
PROPLIST GMPLYP
PVAL WATER 0.0 1.5 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 16. 0.0
RedlichKister
This model calculates activity coefficients. It is a polynomial in the difference
between mole fractions in the mixture. It can be used for liquid and solid
mixtures (mixed crystals).
The equation is:
Where:
nc = Number of components
A
1,ij
= a
ij
/ T + b
ij
A
2,ij
= c
ij
/ T + d
ij
A
3,ij
= e
ij
/ T + f
ij
A
4,ij
= g
ij
/ T + h
ij
A
5,ij
= m
ij
/ T + n
ij
A
n,ii
= A
n,jj
= 0.0
A
n,ji
= A
n,ij
(1)
(n1)
A
n,kj
= A
n,jk
(1)
(n1)
For any component i, the value of the activity coefficient can be fixed:
i
= v
i
2 Thermodynamic Property Models 119
Parameter Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMRKTB/1 a
ij
0 x
GMRKTB/2 b
ij
0 x
GMRKTB/3 c
ij
0 x
GMRKTB/4 d
ij
0 x
GMRKTB/5 e
ij
0 x
GMRKTB/6 f
ij
0 x
GMRKTB/7 g
ij
0 x
GMRKTB/8 h
ij
0 x
GMRKTB/9 m
ij
0 x
GMRKTB/10 n
ij
0 x
GMRKTO v
i
x
ScatchardHildebrand
The ScatchardHildebrand model calculates liquid activity coefficients. It is
used in the CHAOSEA property method and the GRAYSON property method.
The equation for the ScatchardHildebrand model is:
Where:
A
ij
=
i
=
V
m
*,l
=
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
x 5.0 2000.0 TEMPERATURE
DELTA
o
i
x 10
3
10
5
SOLUPARAM
VLCVT1 V
i
*,CVT
x 0.0005 1.0 MOLE
VOLUME
GMSHVL V
i
*,l
x 0.01 1.0 MOLE
VOLUME
GMSHXL k
ij
0.0 x 5 5
120 2 Thermodynamic Property Models
ThreeSuffix Margules
This model can be used to describe the excess properties of liquid and solid
solutions. It does not find much use in chemical engineering applications, but
is still widely used in metallurgical applications. Note that the binary
parameters for this model do not have physical significance.
The equation is:
Where k
ij
is a binary parameter:
For any component i, the value of the activity coefficient can be fixed:
i
= d
i
Parameter Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMMRGB/1 a
ij
0 x TEMPERATURE
GMMRGB/2 b
ij
0 x
GMMRGB/3 c
ij
0 x
GMMRGO d
i
x
References
M. Margules, "ber die Zusammensetzung der gesttigten Dmpfe von
Mischungen," Sitzungsber. Akad. Wiss. Vienna, Vol. 104, (1895), p. 1293.
D.A. Gaskell, Introduction to Metallurgical Thermodyanics, 2nd ed., (New
York: Hemisphere Publishing Corp., 1981), p. 360.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGrawHill, 1987).
UNIFAC Activity Coefficient Model
The UNIFAC model calculates liquid activity coefficients for the following
property methods: UNIFAC, UNIFHOC, and UNIFLL. Because the UNIFAC
model is a groupcontribution model, it is predictive. All published group
parameters and group binary parameters are stored in the Aspen Physical
Property System.
The equation for the original UNIFAC liquid activity coefficient model is made
up of a combinatorial and residual term:
ln
=
ln
i
c
+ ln
i
r
ln
i
c
=
2 Thermodynamic Property Models 121
Where the molecular volume and surface fractions are:
and
Where nc is the number of components in the mixture. The coordination
number z is set to 10. The parameters r
i
and q
i
are calculated from the group
volume and area parameters:
and
Where v
ki
is the number of groups of type k in molecule i, and ng is the
number of groups in the mixture.
The residual term is:
I
k
is the activity coefficient of a group at mixture composition, and I
k
i
is the
activity coefficient of group k in a mixture of groups corresponding to pure i.
The parameters I
k
and I
k
i
are defined by:
With:
And:
The parameter X
k
is the group mole fraction of group k in the liquid:
122 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol DefaultMDS Lower
Limit
Upper
Limit
Units
UFGRP
(k,v
k
, m, v
m
, ...)
GMUFQ Q
k
GMUFR R
k
GMUFB b
kn
TEMPERATURE
The parameter UFGRP stores the UNIFAC functional group number and
number of occurrences of each group. UFGRP is stored in the Aspen Physical
Property System pure component databank for most components. For
nondatabank components, enter UFGRP on the Properties Molecular Structure
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the UNIFAC functional groups.
References
Aa. Fredenslund, J. Gmehling and P. Rasmussen, "VaporLiquid Equilibria
using UNIFAC," (Amsterdam: Elsevier, 1977).
Aa. Fredenslund, R.L. Jones and J.M. Prausnitz, AIChE J., Vol. 21, (1975), p.
1086.
H.K. Hansen, P. Rasmussen, Aa. Fredenslund, M. Schiller, and J. Gmehling,
"VaporLiquid Equilibria by UNIFAC Group Contribution. 5 Revision and
Extension", Ind. Eng. Chem. Res., Vol. 30, (1991), pp. 23522355.
UNIFAC (Dortmund Modified)
The UNIFAC modification by Gmehling and coworkers (Weidlich and
Gmehling, 1987; Gmehling et al., 1993), is slightly different in the
combinatorial part. It is otherwise unchanged compared to the original
UNIFAC:
With:
The temperature dependency of the interaction parameters is:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
UFGRPD
(k,v
k
, m, v
m
, ...)
GMUFDQ Q
k
GMUFDR R
k
UNIFDM/1 a
mn,1
0 TEMPERATURE
2 Thermodynamic Property Models 123
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
UNIFDM/2 a
mn,2
0 TEMPERATURE
UNIFDM/3 a
mn,3
0 TEMPERATURE
The parameter UFGRPD stores the group number and the number of
occurrences of each group. UFGRPD is stored in the Aspen Physical Property
System pure component databank. For nondatabank components, enter
UFGRPD on the Properties Molecular Structure Functional Group sheet. See
Physical Property Data, Chapter 3, for a list of the Dortmund modified UNIFAC
functional groups.
References
U. Weidlich and J. Gmehling, "A Modified UNIFAC Model 1. Prediction of VLE,
h
E
and ," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 13721381.
J. Gmehling, J. Li, and M. Schiller, "A Modified UNIFAC Model. 2. Present
Parameter Matrix and Results for Different Thermodynamic Properties," Ind.
Eng. Chem. Res., Vol. 32, (1993), pp. 178193.
UNIFAC (Lyngby Modified)
The equations for the "temperaturedependent UNIFAC" (Larsen et al., 1987)
are similar to the original UNIFAC:
,
Volume fractions are modified:
With:
Where I
k
and I
k
i
have the same meaning as in the original UNIFAC, but
defined as:
124 2 Thermodynamic Property Models
With:
The temperature dependency of a is described by a function instead of a
constant:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
UFGRPL
(k,v
k
, m, v
m
, ...)
GMUFLQ Q
k
GMUFLR R
k
UNIFLB/1 a
mn,1
0 TEMPERATURE
UNIFLB/2 a
mn,2
0 TEMPERATURE
UNIFLB/3 a
mn,3
0 TEMPERATURE
The parameter UFGRPL stores the modified UNIFAC functional group number
and the number of occurrences of each group. UFGRPL is stored in the Aspen
Physical Property System pure component databank. For nondatabank
components, enter UFGRP on the Properties  Molecular Structure 
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the Larsen modified UNIFAC functional groups.
Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified
UNIFAC GroupContribution Model for Prediction of Phase Equilibria and Heats
of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 2286.
UNIQUAC Activity Coefficient Model
The UNIQUAC model calculates liquid activity coefficients for these property
methods: UNIQUAC, UNIQ2, UNIQHOC, UNIQNTH, and UNIQRK. It is
recommended for highly nonideal chemical systems, and can be used for VLE
and LLE applications. This model can also be used in the advanced equations
of state mixing rules, such as WongSandler and MHV2.
The equation for the UNIQUAC model is:
2 Thermodynamic Property Models 125
Where:
u
i
=
u
i
' =
u
i
=
l
i
=
t
i
' =
t
ij
=
z = 10
a
ij
, b
ij
, c
ij
, and d
ij
are unsymmetrical. That is, a
ij
may not be equal to a
ji
, etc.
Absolute temperature units are assumed for the binary parameters a
ij
, b
ij
, c
ij
,
d
ij
, and e
ij
.
can be determined from VLE and/or LLE data regression. The Aspen Physical
Property System has a large number of builtin parameters for the UNIQUAC
model. The binary parameters have been regressed using VLE and LLE data
from the Dortmund Databank. The binary parameters for VLE applications
were regressed using the ideal gas, RedlichKwong, and HaydenO'Connell
equations of state. See Physical Property Data, Chapter 1, for details.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMUQR r
i
x
GMUQQ q
i
x
GMUQQ1 q
i
' q x
UNIQ/1 a
ij
0 x 50.0 50.0
UNIQ/2 b
ij
0 x 15000.0 15000.0 TEMPERATURE
UNIQ/3 c
ij
0 x TEMPERATURE
UNIQ/4 d
ij
0 x TEMPERATURE
UNIQ/5 T
lower
0 K x TEMPERATURE
UNIQ/6 T
upper
1000 K x TEMPERATURE
UNIQ/7 e
ij
0 x TEMPERATURE
Absolute temperature units are assumed for elements 2 through 4 and 7 of
UNIQ.
126 2 Thermodynamic Property Models
The UNIQ2 property method uses data set 2 for UNIQ. All other UNIQUAC
methods use data set 1.
References
D.S. Abrams and J.M. Prausnitz, "Statistical Thermodynamics of liquid
mixtures: A new expression for the Excess Gibbs Energy of Partly or
Completely Miscible Systems," AIChE J., Vol. 21, (1975), p. 116.
A. Bondi, "Physical Properties of Molecular Crystals, Liquids and Gases," (New
York: Wiley, 1960).
Simonetty, Yee and Tassios, "Prediction and Correlation of LLE," Ind. Eng.
Chem. Process Des. Dev., Vol. 21, (1982), p. 174.
Van Laar Activity Coefficient Model
The Van Laar model (Van Laar 1910) calculates liquid activity coefficients for
the property methods: VANLAAR, VANL2, VANLHOC, VANLNTH, and VANL
RK. It can be used for highly nonideal systems.
Where:
z
i
=
A
i
=
B
i
=
C
i
=
A
ij
=
C
ij
=
C
ij
= C
ji
A
ii
= B
ii
= C
ii
= 0
a
ij
and b
ij
are unsymmetrical. That is, a
ij
may not be equal to a
ji
, and b
ij
may
not be equal to b
ji
.
Parameters
Name/Element
Symbol DefaultMDS Lower Limit Upper
Limit
Units
VANL/1 a
ij
0 x 50.0 50.0
VANL/2 b
ij
0 x 15000.0 15000.0 TEMPERATURE
VANL/3 c
ij
0 x 50.0 50.0
VANL/4 d
ij
0 x 15000.0 15000.0 TEMPERATURE
2 Thermodynamic Property Models 127
The VANL2 property method uses data set 2 for VANL. All other Van Laar
methods use data set 1.
References
J.J. Van Laar, "The Vapor Pressure of Binary Mixtures," Z. Phys. Chem., Vol.
72, (1910), p. 723.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed. (New York: McGrawHill, 1987).
Wagner Interaction Parameter
The Wagner Interaction Parameter model calculates activity coefficients. This
model is used for dilute solutions in metallurgical applications.
The relative activity coefficient with respect to the reference activity
coefficient of a solute i (in a mixture of solutes i, j, and l and solvent A) is:
Where:
The parameter
i
ref
is the reference activity coefficient of solute i:
k
ij
is a binary parameter:
For any component i, the value of the activity coefficient can be fixed:
i
= g
i
This model is recommended for dilute solutions.
Parameter Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
GMWIPR/1 a
i
0 x TEMPERATURE
GMWIPR/2 b
i
0 x
GMWIPR/3 c
i
0 x
GMWIPB/1 d
ij
0 x TEMPERATURE
GMWIPB/2 e
ij
0 x
GMWIPB/3 f
ij
0 x
GMWIPO g
i
x
GMWIPS 0 x
GMWIPS is used to identify the solvent component. You must set GMWIPS to
1.0 for the solvent component. This model allows only one solvent.
128 2 Thermodynamic Property Models
References
A.D. Pelton and C. W. Bale, "A Modified Interaction Parameter Formalism for
NonDilute Solutions," Metallurgical Transactions A, Vol. 17A, (July 1986),
p. 1211.
Wilson Activity Coefficient Model
The Wilson model calculates liquid activity coefficients for the following
property methods: WILSON, WILS2, WILSHOC, WILSNTH, WILSRK, WILS
HF, WILSLR, and WILSGLR. It is recommended for highly nonideal systems,
especially alcoholwater systems. It can also be used in the advanced
equationofstate mixing rules, such as WongSandler and MHV2. This model
cannot be used for liquidliquid equilibrium calculations.
The equation for the Wilson model is:
Where:
ln A
ij
=
WILSON/3 c
ij
0 x  TEMPERATURE
WILSON/4 d
ij
0 x TEMPERATURE
WILSON/5 T
lower
0 K x TEMPERATURE
WILSON/6 T
upper
1000 K x TEMPERATURE
WILSON/7 e
ij
0 x TEMPERATURE
The WILS2 property method uses data set 2 for WILSON. All other Wilson
methods use data set 1.
2 Thermodynamic Property Models 129
In the original formulation of the Wilson model, a
ij
= ln V
j
/V
i
, c
ij
= d
ij
= e
ij
=
0, and
b
ij
= (
ij

ii
)/R, where V
j
and V
i
are pure component liquid molar volume at
25C.
If any of b
iA
, c
iA
, and e
iA
are nonzero, absolute temperature units are
assumed for all coefficients. If b
iA
, c
iA
, and e
iA
are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
References
G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.
Wilson Model with Liquid Molar Volume
This Wilson model (used in the method WILSVOL) calculates liquid activity
coefficients using the original formulation of Wilson (Wilson 1964) except that
liquid molar volume is calculated at system temperature, instead of at 25C.
It is recommended for highly nonideal systems, especially alcohol water
systems. It can be used in any activity coefficient property method or in the
advanced equation of state mixing rules, such as Wong Sandler and MHV2.
This model cannot be used for liquid liquid equilibrium calculations.
The equation for the Wilson model is:
Where:
ln A
ij
=
V
j
and V
i
are pure component liquid molar volume at the system temperature
calculated using the Rackett/DIPPR/IKCAPE model. The extended form of ln
A
ij
provides more flexibility in fitting phase equilibrium and enthalpy data. a
ij
,
b
ij
, c
ij
, d
ij
, and e
ij
are unsymmetrical. That is, a
ij
may not be equal to a
ji
, etc.
The binary parameters a
ij
, b
ij
, c
ij
, d
ij
, and e
ij
must be determined from data
regression of VLE and/or heatofmixing data. There are no built in binary
parameters for this model.
Parameter
Name/Element
SymbolDefault MDS Lower
Limit
Upper
Limit
Units
WSNVOL/1 a
ij
0 x 50.0 50.0
WSNVOL/2 b
ij
0 x 15000.0 15000.0 TEMPERATURE
WSNVOL/3 c
ij
0 x  TEMPERATURE
WSNVOL/4 d
ij
0 x TEMPERATURE
WSNVOL/5 e
ij
0 x TEMPERATURE
is the molar volume for water and is calculated from the ASME steam
table.
V
k
is calculated from the DebyeHckel limiting law for ionic species. It is
assumed to be the infinite dilution partial volume for molecular solutes.
Where:
V
k
w
= Density of water (kg / m
3
)
c
w
= Dielectric constant of water (Fm
1
), a function
of pressure and temperature (Bradley and
Pitzer, 1979)
2 Thermodynamic Property Models 149
Parameter Name Applicable
Components
Symbol Default Units
VLBROC Ions, molecular Solutes
V
k
0 MOLEVOLUME
References
D. J. Bradley, K. S. Pitzer, "Thermodynamics of Electrolytes," J. Phys. Chem.,
83 (12), 1599 (1979).
H.C. Helgeson and D.H. Kirkham, "Theoretical prediction of the
thermodynamic behavior of aqueous electrolytes at high pressure and
temperature. I. Thermodynamic/electrostatic properties of the solvent", Am.
J. Sci., 274, 1089 (1974).
K.S. Pitzer, "Theory: Ion Interaction Approach," Activity Coefficients in
Electrolyte Solutions, Pytkowicz, R. ed., Vol. I, (CRC Press Inc., Boca Raton,
Florida, 1979).
Liquid Constant Molar Volume Model
This model, VL0CONS, uses a constant value entered by the user as the pure
component liquid molar volume. It is not a function of temperature or
pressure. This is used with the solids handling property method for modeling
nonconventional solids.
Parameter Name Default MDS Units
VLCONS 1 x MOLEVOLUME
Rackett/DIPPR/PPDS/IKCAPE Liquid
Molar Volume
The Aspen Physical Property System has several submodels for calculating
liquid molar volume. It uses parameter THRSWT/2 to determine which
submodel is used. See Pure Component TemperatureDependent Properties
for details.
If THRSWT/2 is This equation is used And this parameter is used
0 Rackett RKTZRA
100116 DIPPR DNLDIP
301 PPDS DNLPDS
401 IKCAPE VLPO
503 NIST ThermoML
Polynomial
DNLTMLPO
504 NIST TDE expansion DNLEXSAT
514 NIST TDE Rackett DNLRACK
515 NIST COSTALD DNLCOSTD
For liquid molar volume of mixtures, the Rackett mixture equation is always
used by default. This is not necessarily consistent with the pure component
molar volume or density. If you need consistency, select route VLMX26 on the
150 2 Thermodynamic Property Models
Properties  Property Methods form. This route calculates mixture molar
volume from the molefraction average of pure component molar volumes.
Many of these equations calculate density first, and return calculate liquid
molar volume based on that density:
DIPPR
DIPPR equation 105 is the default DIPPR equation for most substances:
This equation is similar to the Rackett equation.
DIPPR equation 116 is the default equation for water.
t = 1  T / T
c
Other DIPPR equations, such as equation 100, may be used for some
substances. Check the value of THRSWT/2 to determine the equation used.
See Pure Component TemperatureDependent Properties for details about
DIPPR equations.
In either case, linear extrapolation of
i
*,l
versus T occurs outside of
temperature bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNLDIP/1 C
1i
x MOLEDENSITY
DNLDIP/2 C
2i
0 x
DNLDIP/3 C
3i
T
ci
x TEMPERATURE
DNLDIP/4 C
4i
0 x
DNLDIP/5 C
5i
0 x
DNLDIP/6 C
6i
0 x TEMPERATURE
DNLDIP/7 C
7i
1000 x TEMPERATURE
For equation 116, the units are MOLEDENSITY for parameters DNLDIP/1
through DNLDIP/5 and the default for DNLDIP/3 is 0. For equation 105,
DNLDIP/5 is not used, and absolute temperature units are assumed for
DNLDIP/3.
PPDS
The PPDS equation is:
2 Thermodynamic Property Models 151
Linear extrapolation of
i
*,l
versus T occurs outside of temperature bounds.
Parameter
Name/Element
Symbol DefaultMDS Lower
Limit
Upper
Limit
Units
MW M
i
1.0 5000.0
VC V
ci
0.001 3.5 MOLEVOLUME
TC T
ci
5.0 2000.0 TEMPERATURE
DNLPDS/1 C
1i
MASSDENSITY
DNLPDS/2 C
2i
0 MASSDENSITY
DNLPDS/3 C
3i
0 MASSDENSITY
DNLPDS/4 C
4i
0 MASSDENSITY
DNLPDS/5 C
5i
0 x TEMPERATURE
DNLPDS/6 C
6i
1000 x TEMPERATURE
IKCAPE
The IKCAPE equation is:
Linear extrapolation of V
i
*,l
versus T occurs outside of temperature bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
VLPO/1 C
1i
X MOLE
VOLUME
VLPO/2, ..., 10 C
2i
, ..., C
10i
0 X MOLE
VOLUME
TEMPERATURE
VLPO/11 C
11i
0 X TEMPERATURE
VLPO/12 C
12i
1000 X TEMPERATURE
NIST ThermoML Polynomial
This equation can be used when parameter DNLTMLPO is available.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNLTMLPO/1 C
1i
X MOLE
DENSITY
DNLTMLPO/2, 3,
4
C
2i
, C
3i
, C
4i
0 X MOLE
DENSITY
TEMPERATURE
DNLTMLPO/5 nTerms 4 X
DNLTMLPO/6 0 X TEMPERATURE
DNLTMLPO/7 1000 X TEMPERATURE
152 2 Thermodynamic Property Models
Rackett
The Rackett equation is:
Where:
T
r
= T / T
ci
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
RKTZRA Z
i
*,RA
ZC x 0.1 1.0
NIST TDE Rackett Parameters
This equation can be used when the parameter DNLRACK is available.
Linear extrapolation of V
i
*,l
versus T occurs outside of temperature bounds.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNLRACK/1 Z
c
x
DNLRACK/2 n 2/7 x
DNLRACK/3 T
ci
x TEMPERATURE
DNLRACK/4 p
ci
0 x PRESSURE
DNLRACK/5 T
lower
0 x TEMPERATURE
DNLRACK/6 T
upper
1000 x TEMPERATURE
NIST COSTALD Parameters
This equation can be used when the parameter DNLCOSTD is available.
2 Thermodynamic Property Models 153
Linear extrapolation of V
i
*,l
versus T occurs outside of temperature bounds.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNLCOSTD/1 V
oi
x VOLUME
DNLCOSTD/2
O
0 x
DNLCOSTD/3 T
ci
x TEMPERATURE
DNLCOSTD/4 T
lower
0 x TEMPERATURE
DNLCOSTD/5 T
upper
1000 x TEMPERATURE
NIST TDE Expansion
This equation can be used when the parameter DNLEXSAT is available.
Linear extrapolation of V
i
*,l
versus T occurs outside of temperature bounds.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNLEXSAT/1
ci
x MOLE
DENSITY
DNLEXSAT/2 C
1i
x MOLE
DENSITY
DNLEXSAT/3,
..., DNLEXSAT/7
C
2i
, ..., C
6i
0 x MOLE
DENSITY
DNLEXSAT/8 T
ci
x TEMPERATURE
DNLEXSAT/9 nTerms 6 x
DNLEXSAT/10 T
lower
0 x TEMPERATURE
DNLEXSAT/11 T
upper
1000 x TEMPERATURE
References
H.G. Rackett, J.Chem. Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.
154 2 Thermodynamic Property Models
Rackett/CampbellThodos Mixture Liquid
Volume
The Rackett equation calculates liquid molar volume for all activity coefficient
based and petroleum tuned equation of state based property methods. In the
last category of property methods, the equation is used in conjunction with
the API model. The API model is used for pseudocomponents, while the
Rackett model is used for real components. (See API Liquid Volume .)
CampbellThodos is a variation on the Rackett model which allows the
compressibility term Z
i
*,RA
to vary with temperature.
Rackett
The equation for the Rackett model is:
Where:
T
c
=
=
Z
m
RA
=
V
cm
=
T
r
= T / T
c
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
VCRKT V
ci
VC x 0.001 3.5 MOLE
VOLUME
RKTZRA Z
i
*,RA
ZC x 0.1 1.0
RKTKIJ k
ij
x 5.0 5.0
2 Thermodynamic Property Models 155
CampbellThodos
The CampbellThodos model uses the same equation and parameters as the
Rackett model, above, except that Z
m
RA
is allowed to vary with temperature:
Z
m
RA
=
CampbellThodos also uses separatelyadjustable versions of the critical
parameters. Tmin and Tmax define the temperature range where the
equation is applicable.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
RACKET/1 R*T
ci
/P
ci
R*Tci/Pci MOLE
VOLUME
RACKET/2 Z
i
*,RA
RKTZRA x 0.1 1.0
RACKET/3 d
i
0 x 0 0.11
RACKET/4 T
min
0 x TEMPERATURE
RACKET/5 T
max
1000 x TEMPERATURE
The CampbellThodos model is used when RACKET/3 is set to a value less
than 0.11. The default value, 2/7, indicates that the standard Rackett
equation should be used. When CampbellThodos is not used, RACKET/3
should be kept at its default value of 2/7 for all components.
References
H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.
Modified Rackett Liquid Molar Volume
The Modified Rackett equation improves the accuracy of liquid mixture molar
volume calculation by introducing additional parameters to compute the pure
component parameter RKTZRA and the binary parameter k
ij
.
The equation for the Modified Rackett model is:
Where:
T
c
=
k
ij
=
156 2 Thermodynamic Property Models
=
Z
m
RA
=
Z
i
*,RA
=
V
cm
=
T
r
= T / T
c
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
MRKZRA/1 a
i
RKTZRA x 0.1 0.5
MRKZRA/2 b
i
0 x
MRKZRA/3 c
i
0 x
MRKKIJ/1 A
ij
x
MRKKIJ/2 B
ij
0 x
MRKKIJ/3 C
ij
0 x
References
H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.
Aspen/DIPPR/IKCAPE Solid Molar Volume
The Aspen Physical Property System has several submodels for calculating
solid molar volume. It uses parameter THRSWT/1 to determine which
submodel is used. See Pure Component TemperatureDependent Properties
for details.
If THRSWT/1 is This equation is used And this parameter is
used
0 Aspen VSPOLY
100 DIPPR DNSDIP
401 IKCAPE VSPO
503 NIST ThermoML
polynomial
DNSTMLPO
2 Thermodynamic Property Models 157
Aspen Polynomial
The equation for the Aspen solids volume polynomial is:
Linear extrapolation of V
i
*,s
versus T occurs outside of temperature bounds.
Parameter
Name
Applicable
Components
Symbol MDS Default Units
VSPOLY/1 Salts, CI solids C
1i
x MOLEVOLUME
TEMPERATURE
VSPOLY/2, ..., 5 Salts, CI solids C
2i
, ..., C
5i
x 0 MOLEVOLUME
TEMPERATURE
VSPOLY/6 Salts, CI solids C
6i
x 0 MOLEVOLUME
TEMPERATURE
VSPOLY/7 Salts, CI solids C
7i
x 1000 MOLEVOLUME
TEMPERATURE
IKCAPE Equation
The IKCAPE equation is:
Linear extrapolation of V
i
*,s
versus T occurs outside of temperature bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
VSPO/1 C
1i
X MOLE
VOLUME
VSPO/2, ..., 10 C
2i
, ..., C
10i
0 X MOLE
VOLUME
TEMPERATURE
VSPO/11 C
11i
0 X TEMPERATURE
VSPO/12 C
12i
1000 X TEMPERATURE
DIPPR
The DIPPR equation is:
Linear extrapolation of
i
*,s
versus T occurs outside of temperature bounds.
V
i
*,s
= 1 /
i
*,s
(Other DIPPR equations may sometimes be used. See Pure Component
TemperatureDependent Properties for details.)
The model returns solid molar volume for pure components.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNSDIP/1 C
1i
x MOLE
158 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DENSITY
DNSDIP/2, ..., 5 C
2i
, ..., C
5i
0 x MOLE
DENSITY,
TEMPERATURE
DNSDIP/6 C
6i
0 x TEMPERATURE
DNSDIP/7 C
7i
1000 x TEMPERATURE
NIST ThermoML Polynomial
Linear extrapolation of
i
*,s
versus T occurs outside of temperature bounds.
V
i
*,s
= 1 /
i
*,s
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
DNSTMLPO/1 C
1i
x MOLE
DENSITY
DNSTMLPO/2,...,8 C
2i
, ..., C
8i
0 x MOLE
DENSITY,
TEMPERATURE
DNSTMLPO/9 nTerms 8 x
DNSTMLPO/10 T
lower
0 x TEMPERATURE
DNSTMLPO/11 T
upper
1000 x TEMPERATURE
Liquid Volume Quadratic Mixing Rule
With i and j being components, the liquid volume quadratic mixing rule is:
Option Codes
Option Code Value Descriptions
1 0 Use normal pure component liquid volume model for all
components (default)
1 Use steam tables for water
2 0 Use mole basis composition (default)
1 Use mass basis composition
Parameter
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
VLQKIJ K
ij
 x  
2 Thermodynamic Property Models 159
Heat Capacity Models
The Aspen Physical Property System has five builtin heat capacity models.
This section describes the heat capacity models available.
Model Type
Aqueous Infinite Dilution Heat Capacity
Polynomial
Electrolyte liquid
CrissCobble Aqueous Infinite Dilution
Ionic Heat Capacity
Electrolyte liquid
DIPPR/IKCAPE Liquid Heat Capacity Liquid
Aspen/DIPPR/Barin/IKCAPE Ideal Gas
Heat Capacity
Ideal gas
Aspen/DIPPR/Barin/IKCAPE Solid Heat
Capacity
Solid
Aqueous Infinite Dilution Heat Capacity
The aqueous phase infinite dilution enthalpies, entropies, and Gibbs energies
are calculated from the heat capacity polynomial. The values are used in the
calculation of aqueous and mixed solvent properties of electrolyte solutions:
versus T is linearly extrapolated using the slope at C
7i
for T < C
7i
versus T is linearly extrapolated using the slope at C
8i
for T < C
8i
Parameter
Name/Element
Applicable
Components
Symbol Default Units
CPAQ0/1 Ions, molecular solutes C
1i
TEMPERATURE and
HEAT CAPACITY
CPAQ0/2,,6 Ions, molecular solutes C
2i
, ..., C
6i
0 TEMPERATURE and
HEAT CAPACITY
CPAQ0/7 Ions, molecular solutes C
7i
0 TEMPERATURE
CPAQ0/8 Ions, molecular solutes C
8i
1000 TEMPERATURE
If any of C
4i
through C
6i
is nonzero, absolute temperature units are
assumed for C
1i
through C
6i
. Otherwise, user input units for temperature are
used. The temperature limits are always interpreted in user input units.
160 2 Thermodynamic Property Models
CrissCobble Aqueous Infinite Dilution Ionic
Heat Capacity
The CrissCobble correlation for aqueous infinite dilution ionic heat capacity is
used if no parameters are available for the aqueous infinite dilution heat
capacity polynomial. From the calculated heat capacity, the thermodynamic
properties entropy, enthalpy and Gibbs energy at infinte dilution in water are
derived:
Parameter
Name
Applicable
Components
Symbol Default Units
IONTYP Ions Ion Type 0
SO25C Anions MOLEENTROPY
Cations MOLEENTROPY
DIPPR/PPDS/IKCAPE Liquid Heat Capacity
The Aspen Physical Property System has several submodels for calculating
liquid heat capacity. It uses parameter THRSWT/6 to determine which
submodel is used. See Pure Component TemperatureDependent Properties
for details.
If THRSWT/6 is This equation is used And this parameter is used
100 DIPPR CPLDIP
200 Barin CPLXP1, CPLXP2
301 PPDS CPLPDS
401 IKCAPE heat capacity
polynomial
CPLPO
403 IKCAPE liquid heat
capacity
CPLIKC
503 NIST ThermoML
polynomial
CPLTMLPO
506 NIST TDE equation CPLTDECS
The DIPPR/PPDS/IKCAPE liquid heat capacity model is used to calculate pure
component liquid heat capacity and pure component liquid enthalpy. To use
this model, two conditions must exist:
 One of the parameters for calculating heat capacity (see table below) is
available.
 The component is not supercritical (HENRYCOMP).
The model uses a specific method (see Methods in Property Calculation
Methods and Routes):
2 Thermodynamic Property Models 161
Where
= Reference enthalpy calculated at T
ref
= Ideal gas enthalpy
= Vapor enthalpy departure
= Enthalpy of vaporization
T
ref
is the reference temperature; it defaults to 298.15 K. You can enter a
different value for the reference temperature. This is useful when you want to
use this model for very light components or for components that are solids at
298.15K.
Activate this model by specifying the route DHL09 for the property DHL on
the Properties Property Methods Routes sheet. For equation of state property
method, you must also modify the route for the property DHLMX to use a
route with method 2 or 3, instead of method 1. For example, you can use the
route DHLMX00 or DHLMX30. You must ascertain that the route for DHLMX
that you select contains the appropriate vapor phase model and heat of
mixing calculations. Click the View button on the form to see details of the
route.
Optionally, you can specify that this model is used for only certain
components. The properties for the remaining components are then
calculated by the standard model. Use the parameter COMPHL to specify the
components for which this model is used. By default, all components with the
CPLDIP or CPLIKC parameters use this model.
DIPPR Liquid Heat Capacity
The DIPPR equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 100.
The DIPPR equation is:
Linear extrapolation occurs for C
p
*,l
versus T outside of bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLDIP/1 C
1i
x MOLEHEAT
CAPACITY,
TEMPERATURE
CPLDIP/2, ..., 5 C
2i
, ..., C
5i
0 x MOLEHEAT
CAPACITY,
TEMPERATURE
162 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLDIP/6 C
6i
0 x TEMPERATURE
CPLDIP/7 C
7i
1000 x TEMPERATURE
TREFHL T
ref
298.15 TEMPERATURE
COMPHL
To specify that the model is used for a component, enter a value of 1.0 for
COMPHL.
(Other DIPPR equations may sometimes be used. See Pure Component
TemperatureDependent Properties for details.)
PPDS Liquid Heat Capacity
The PPDS equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 301.
The PPDS equation is:
Where R is the gas constant.
Linear extrapolation occurs for C
p
*,l
versus T outside of bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLPDS/1 C
1i
CPLPDS/2 C
2i
0
CPLPDS/3 C
3i
0
CPLPDS/4 C
4i
0
CPLPDS/5 C
5i
0
CPLPDS/6 C
6i
0
CPLPDS/7 C
7i
0 x TEMPERATURE
CPLPDS/8 C
8i
1000 x TEMPERATURE
IKCAPE Liquid Heat Capacity
Two IKCAPE equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for C
p
*,l
versus T outside of bounds for either equation.
When THRSWT/6 is 403, the IKCAPE liquid heat capacity equation is used.
The equation is:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
2 Thermodynamic Property Models 163
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLIKC/1 C
1i
T
x MOLEHEAT
CAPACITY
CPLIKC/2,...,4 C
2i
, ..., C
4i
0 x MOLEHEAT
CAPACITY,
TEMPERATURE
CPLIKC/5 C
5i
0 x MOLEHEAT
CAPACITY,
TEMPERATURE
CPLIKC/6 C
6i
0 x TEMPERATURE
CPLIKC/7 C
7i
1000 x TEMPERATURE
If C
5i
is nonzero, absolute temperature units are assumed for C
2i
through
C
5i
. Otherwise, user input units for temperature are used. The temperature
limits are always interpreted in user input units.
When THRSWT/6 is 401, the IKCAPE heat capacity polynomial is used.The
equation is:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLPO/1 C
1i
X MOLECAPACITY
CPLPO/2,,10 C
2i
, ..., C
10i
0 X MOLECAPACITY
TEMPERATURE
CPLPO/11 C
11i
0 X TEMPERATURE
CPLPO/12 C
12i
1000 X TEMPERATURE
See Pure Component TemperatureDependent Properties for details on the
THRSWT parameters.
NIST Liquid Heat Capacity
Two NIST equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for C
p
*,l
versus T outside of bounds for either equation.
When THRSWT/6 is 503, the ThermoML polynomial is used to calculate liquid
heat capacity:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLTMLPO/1 C
1i
X J/K^2/mol
CPLTMLPO/2,,5 C
2i
, ..., C
5i
0 X J/K^2/mol
CPLTMLPO/6 nTerms 5 X
CPLTMLPO/7 T
lower
0 X TEMPERATURE
164 2 Thermodynamic Property Models
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLTMLPO/8 T
upper
1000 X TEMPERATURE
When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat
capacity:
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLTDECS/1 C
1i
X MOLEHEAT
CAPACITY
CPLTDECS/2,,4 C
2i
, ..., C
4i
0 X MOLEHEAT
CAPACITY
CPLTDECS/5 B 0 X MOLEHEAT
CAPACITY
CPLTDECS/6 T
ci
X TEMPERATURE
CPLTDECS/7 nTerms 4 X
CPLTDECS/8 T
lower
0 X TEMPERATURE
CPLTDECS/9 T
upper
1000 X TEMPERATURE
See Pure Component TemperatureDependent Properties for details on the
THRSWT parameters.
Aspen/DIPPR/Barin/PPDS/IKCAPE Ideal
Gas Heat Capacity
The Aspen Physical Property System has several submodels for calculating
ideal gas heat capacity. It uses parameter THRSWT/7 to determine which
submodel is used. See Pure Component TemperatureDependent Properties
for details.
If THRSWT/7 is This equation is used And this parameter is
used
0 Ideal gas heat capacity
polynomial
CPIG
107 DIPPR CPIGDP
200 Barin CPIXP1, CPIXP2, CPIXP3
301 PPDS CPIGDS
401 IKCAPE heat capacity
polynomial
CPIGPO
503 NIST ThermoML
polynomial
CPITMLPO
513 NIST AlyLee CPIALEE
These equations are also used to calculate ideal gas enthalpies, entropies,
and Gibbs energies.
2 Thermodynamic Property Models 165
Aspen Ideal Gas Heat Capacity Polynomial
The ideal gas heat capacity polynomial is available for components stored in
ASPENPCD, AQUEOUS, and SOLIDS databanks. This model is also used in
PCES.
C
p
*,ig
is linearly extrapolated using slope at
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIG/1 C
1i
MOLEHEATCAPACITY,
TEMPERATURE
CPIG/2, ..., 6 C
2i
, ..., C
6i
0 MOLEHEATCAPACITY,
TEMPERATURE
CPIG/7 C
7i
0 TEMPERATURE
CPIG/8 C
8i
1000 TEMPERATURE
CPIG/9, 10,
11
C
9i
, C
10i
, C
11i
MOLEHEATCAPACITY,
TEMPERATURE
If C
10i
or C
11i
is nonzero, then absolute temperature units are assumed for
C
9i
through C
11i
. Otherwise, user input temperature units are used for all
parameters. User input temperature units are always used for C
1i
through C
8i
.
NIST ThermoML Polynomial
This equation can be used when parameter CPITMLPO is available.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPITMLPO /1 C
1i
x J/K^2/mol
CPITMLPO /2,
..., 6
C
2i
, ..., C
6i
0 x J/K^2/mol
CPITMLPO/7 nTerms 6 x
CPITMLPO /8 T
lower
0 x TEMPERATURE
CPITMLPO /9 T
upper
1000 x TEMPERATURE
DIPPR
The DIPPR ideal gas heat capacity equation by Aly and Lee 1981 is:
No extrapolation is used with this equation.
166 2 Thermodynamic Property Models
(Other DIPPR equations may sometimes be used. See Pure Component
TemperatureDependent Properties for details.)
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIGDP/1 C
1i
x MOLEHEAT
CAPACITY
CPIGDP/2 C
2i
0 x MOLEHEAT
CAPACITY
CPIGDP/3 C
3i
0 x TEMPERATURE
CPIGDP/4 C
4i
0 x MOLEHEAT
CAPACITY
CPIGDP/5 C
5i
0 x TEMPERATURE
CPIGDP/6 C
6i
0 x TEMPERATURE
CPIGDP/7 C
7i
1000 x TEMPERATURE
Absolute temperature units are assumed for C
3i
and C
5i
. The temperature
limits are always interpreted in user input units.
NIST AlyLee
This equation is the same as the DIPPR Aly and Lee equation above, but it
uses a different parameter set. Note that elements 6 and 7 of the CPIALEE
parameter are not used in the equation.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIALEE/1 C
1i
x MOLEHEAT
CAPACITY
CPIALEE/2 C
2i
0 x MOLEHEAT
CAPACITY
CPIALEE/3 C
3i
0 x TEMPERATURE
CPIALEE/4 C
4i
0 x MOLEHEAT
CAPACITY
CPIALEE/5 C
5i
0 x TEMPERATURE
CPIALEE/8 C
6i
0 x TEMPERATURE
CPIALEE/9 C
7i
1000 x TEMPERATURE
Absolute temperature units are assumed for C
3i
and C
5i
. The temperature
limits are always interpreted in user input units.
PPDS
The PPDS equation is:
where R is the gas constant.
2 Thermodynamic Property Models 167
Linear extrapolation of C
p
*,ig
versus T is performed outside temperature
bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIGDS/1 C
1i
TEMPERATURE
CPIGDS/2, , 8 C
2i
, ..., C
8i
0
CPIGDS/9 C
9i
0 TEMPERATURE
CPIGDS/10 C
10i
1000 TEMPERATURE
IKCAPE Heat Capacity Polynomial
The equation is:
Linear extrapolation of C
p
*,ig
versus T is performed outside temperature
bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIGPO/1 C
1i
X MOLECAPACITY
CPIGPO/2,,10 C
2i
, ..., C
10i
0 X MOLECAPACITY
TEMPERATURE
CPIGPO/11 C
11i
0 X TEMPERATURE
CPIGPO/12 C
12i
1000 X TEMPERATURE
References
Data for the Ideal Gas Heat Capacity Polynomial: Reid, Prausnitz and Poling,
The Properties of Gases and Liquids, 4th ed., (New York: McGrawHill, 1987).
The Aspen Physical Property System combustion data bank, JANAF
Thermochemical Data, Compiled and calculated by the Thermal Research
Laboratory of Dow Chemical Company.
F. A. Aly and L. L. Lee, "SelfConsistent Equations for Calculating the Ideal
Gas Heat Capacity, Enthalpy, and Entropy, Fluid Phase Eq., Vol. 6, (1981), p.
169.
Aspen/DIPPR/Barin/IKCAPE Solid Heat
Capacity
The Aspen Physical Property System has several submodels for calculating
solid heat capacity. It uses parameter THRSWT/5 to determine which
submodel is used. See Pure Component TemperatureDependent Properties
for details.
168 2 Thermodynamic Property Models
If THRSWT/5 is This equation is used And this parameter is
used
0 Aspen solid heat capacity
polynomial
CPSPO1
100 DIPPR CPSDIP
200 Barin CPSXP1, CPSXP2, ,
CPSXP7
401 IKCAPE heat capacity
polynomial
CPSPO
503 NIST ThermoML
polynomial
CPSTMLPO
The enthalpy, entropy, and Gibbs energy of solids are also calculated from
these equations:
Aspen Solid Heat Capacity Polynomial
The Aspen equation is:
Linear extrapolation occurs for C
p,i
*,s
versus T outside of bounds.
Parameter
Name
Applicable
Components
Symbol MDS Default Units
CPSPO1/1 Solids, Salts C
1i
x
CPSPO1/2, ..., 6 Solids, Salts C
2i
, ..., C
6i
x 0
CPSPO1/7 Solids, Salts C
7i
x 0
CPSPO1/8 Solids, Salts C
8i
x 1000
The units are TEMPERATURE and HEATCAPACITY for all elements. If any of
C
4i
through C
6i
are nonzero, absolute temperature units are assumed for
elements C
1i
through C
6i
. Otherwise, user input temperature units are
assumed for all elements. The temperature limits are always interpreted in
user input units.
DIPPR
The DIPPR equation is:
Linear extrapolation occurs for C
p,i
*,s
versus T outside of bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPSDIP/1 C
1i
x MOLEHEAT
CAPACITY,
TEMPERATURE
CPSDIP/2,...,5 C
2i
, ..., C
5i
0 x MOLEHEAT
CAPACITY,
TEMPERATURE
CPSDIP/6 C
6i
0 x TEMPERATURE
CPSDIP/7 C
7i
1000 x TEMPERATURE
2 Thermodynamic Property Models 169
(Other DIPPR equations may sometimes be used. See Pure Component
TemperatureDependent Properties for details.)
NIST ThermoML Polynomial
The equation is:
Linear extrapolation occurs for C
p,i
*,s
versus T outside of bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPSTMLPO/1 C
1i
x J/K^2/mol
CPSTMLPO/2,...,5C
2i
, ..., C
5i
0 x J/K^2/mol
CPSTMLPO/6 nTerms 5 x
CPSTMLPO/7 T
lower
0 x TEMPERATURE
CPSTMLPO/8 T
upper
1000 x TEMPERATURE
IKCAPE Heat Capacity Polynomial
The equation is:
Linear extrapolation occurs for C
p,i
*,s
versus T outside of bounds.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPSPO/1 C
1i
X MOLECAPACITY
CPSPO/2,,10 C
10i
0 X MOLECAPACITY
TEMPERATURE
CPSPO/11 C
11i
0 X TEMPERATURE
CPSPO/12 C
12i
1000 X TEMPERATURE
Solubility Correlations
The Aspen Physical Property System has three builtin solubility correlation
models. This section describes the solubility correlation models available.
Model Type
Henry's constant Gas solubility in liquid
Water solubility Water solubility in organic liquid
Hydrocarbon solubility Hydrocarbon solubility in waterrich
liquid
170 2 Thermodynamic Property Models
Henry's Constant
The Henry's constant model is used when Henry's Law is applied to calculate
Kvalues for dissolved gas components in a mixture. Henry's Law is available
in all activity coefficient property methods, such as the WILSON property
method. The model calculates Henry's constant for a dissolved gas component
(i) in one or more solvents (A or B):
Where:
w
A
=
ln H
iA
(T, p
A
*,l
) =
Linear extrapolation occurs for ln H
iA
versus T outside of bounds.
H
iA
(T, P) =
The parameter is obtained from the BrelviO'Connell model. p
A
*,l
is
obtained from the Antoine model. is obtained from the appropriate activity
coefficient model.
The Henry's constants a
iA
, b
iA
, c
iA
, d
iA
, and e
iA
are specific to a solutesolvent
pair. They can be obtained from regression of gas solubility data. The Aspen
Physical Property System has a large number of builtin Henry's constants for
many solutes in solvents. These parameters were obtained using data from
the Dortmund Databank. See Physical Property Data, Chapter 1, for details.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
VC V
cA
0.001 3.5 MOLEVOLUME
HENRY/1 a
iA
x PRESSURE,
TEMPERATURE
HENRY/2 b
iA
0 x TEMPERATURE
HENRY/3 c
iA
0 x TEMPERATURE
HENRY/4 d
iA
0 x TEMPERATURE
HENRY/5 T
L
0 x TEMPERATURE
HENRY/6 T
H
2000 x TEMPERATURE
HENRY/7 e
iA
0 x TEMPERATURE
If any of b
iA
, c
iA
, and e
iA
are nonzero, absolute temperature units are
assumed for all coefficients. If b
iA
, c
iA
, and e
iA
are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
2 Thermodynamic Property Models 171
If a
iA
is missing, is set to zero and the weighting factor w
A
is
renormalized.
Water Solubility
This model calculates solubility of water in a hydrocarbonrich liquid phase.
The model is used automatically when you model a hydrocarbonwater
system with the freewater option. See FreeWater Immiscibility Simplification
in FreeWater and ThreePhase Calculations for details.
The expression for the liquid mole fraction of water in the ith hydrocarbon
species is:
No extrapolation is used with this equation.
The parameters for about 60 components are stored in the Aspen Physical
Property System pure component databank.
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
WATSOL/1 C
1i
fcn(T
bi
, SG
i
, M
i
) 10.0 33.0
WATSOL/2 C
2i
fcn(T
bi
, SG
i
, M
i
) 10000.0 3000.0 TEMPERATURE
WATSOL/3 C
3i
0 0.05 0.05 TEMPERATURE
WATSOL/4 C
4i
0 0.0 500 TEMPERATURE
WATSOL/5 C
5i
1000 4.0 1000 TEMPERATURE
Absolute temperature units are assumed for elements 2 through 5.
Hydrocarbon Solubility
This model calculates solubility of hydrocarbon in a waterrich liquid phase.
The model is used automatically when you model a hydrocarbonwater
system with the dirtywater option. See FreeWater Immiscibility
Simplification in FreeWater and Rigorous ThreePhase Calculations for
details.
The expression for the liquid mole fraction of the ith hydrocarbon species in
water is:
No extrapolation is used with this equation.
The parameters for about 40 components are stored in the Aspen Physical
Property System pure component databank.
172 2 Thermodynamic Property Models
Parameter
Name/
Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
HCSOL/1 C
1i
fcn(carbon
number)
1000.0 1000.0
HCSOL/2 C
2i
0 
100000.0
100000.0 TEMPERATURE
HCSOL/3 C
3i
0 100.0 100.0 TEMPERATURE
HCSOL/4 C
4i
0 0.0 500 TEMPERATURE
HCSOL/5 C
5i
1000 4.0 1000 TEMPERATURE
For Hydrocarbons and pseudocomponents, the default values are estimated
by the method given by API Procedure 9A2.17 at 25 C.
Absolute temperature units are assumed for elements 2 and 3. The
temperature limits are always interpreted in user input units.
Reference
C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185206.
Other Thermodynamic Property
Models
The Aspen Physical Property System has some builtin additional
thermodynamic property models that do not fit in any other category. This
section describes these models:
 Cavett Liquid Enthalpy Departure
 Barin Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity
 Electrolyte NRTL Enthalpy
 Electrolyte NRTL Gibbs Energy
 Liquid Enthalpy from Liquid Heat Capacity Correlation
 Enthalpies Based on Different Reference States
 Helgeson Equations of State
 Quadratic Mixing Rule
Cavett
The general form for the Cavett model is:
2 Thermodynamic Property Models 173
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
TC T
ci
5.0 2000.0 TEMPERATURE
PC p
ci
10
5
10
8
PRESSURE
DHLCVT ZC X 0.1 0.5
Barin Equations for Gibbs Energy, Enthalpy,
Entropy, and Heat Capacity
The following equations are used when parameters from the Aspen Physical
Property System inorganic databank are retrieved.
 Gibbs energy:
(1)
 Enthalpy:
(2)
 Entropy:
(3)
 Heat capacity:
(4)
o refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each
phase, multiple sets of parameters from 1 to n are present to cover multiple
temperature ranges. The value of the parameter n depends on the phase.
(See tables that follow.) When the temperature is outside all these
temperature ranges, linear extrapolation of properties versus T is performed
using the slope at the end of the nearest temperature bound.
The four properties C
p
, H, S, and G are interrelated as a result of the
thermodynamic relationships:
There are analytical relationships between the expressions describing the
properties C
p
, H, S, and G (equations 1 to 4). The parameters a
n,i
to h
n,i
can
occur in more than one equation.
The Aspen Physical Property System has other models which can be used to
calculate temperaturedependent properties which the BARIN equations can
174 2 Thermodynamic Property Models
calculate. The Aspen Physical Property System uses the parameters in
THRSWT to determine which model is used. See Pure Component
TemperatureDependent Properties for details.
If this parameter is 200 Then the BARIN equations are
used to calculate
THRSWT/3 Liquid vapor pressure
THRSWT/5 Solid heat capacity
THRSWT/6 Liquid heat capacity
THRSWT/7 Ideal gas heat capacity
Solid Phase
The parameters in range n are valid for temperature: T
n,l
s
< T < T
n,h
s
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name
/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPSXPn/1 T
n,l
s
x TEMPERATURE
CPSXPn/2 T
n,h
s
x TEMPERATURE
CPSXPn/3 a
n,i
s
x
CPSXPn/4 b
n,i
s
0 x
CPSXPn/5 c
n,i
s
0 x
CPSXPn/6 d
n,i
s
0 x
CPSXPn/7 e
n,i
s
0 x
CPSXPn/8 f
n,i
s
0 x
CPSXPn/9 g
n,i
s
0 x
CPSXPn/10 h
n,i
s
0 x
n is 1 through 7. CPSXP1 vector stores solid parameters for the first
temperature range. CPSXP2 vector stores solid parameters for the second
temperature range, and so on.
TEMPERATURE, ENTHALPY, ENTROPY
Liquid Phase
The parameters in range n are valid for temperature: T
n,l
l
< T < T
n,h
l
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name
/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLXPn/1 T
n,l
l
x TEMPERATURE
CPLXPn/2 T
n,h
l
x TEMPERATURE
CPLXPn/3 a
n,i
l
x
CPLXPn/4 b
n,i
l
0 x
CPLXPn/5 c
n,i
l
0 x
CPLXPn/6 d
n,i
l
0 x
CPLXPn/7 e
n,i
l
0 x
CPLXPn/8 f
n,i
l
0 x
2 Thermodynamic Property Models 175
Parameter Name
/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPLXPn/9 g
n,i
l
0 x
CPLXPn/10 h
n,i
l
0 x
n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature
range. CPLXP2 stores liquid parameters for the second temperature range.
TEMPERATURE, ENTHALPY, ENTROPY
Ideal Gas Phase
The parameters in range n are valid for temperature: T
n,l
ig
< T < T
n,h
ig
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name
/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIXPn/1 T
n,l
ig
x TEMPERATURE
CPIXPn/2 T
n,h
ig
x TEMPERATURE
CPIXPn/3 a
n,i
ig
x
CPIXPn/4 b
n,i
ig
0 x
CPIXPn/5 c
n,i
ig
0 x
CPIXPn/6 d
n,i
ig
0 x
CPIXPn/7 e
n,i
ig
0 x
CPIXPn/8 f
n,i
ig
0 x
CPIXPn/9 g
n,i
ig
0 x
CPIXPn/10 h
n,i
ig
0 x
n is 1 through 3. CPIXP1 vector stores ideal gas parameters for the first
temperature range. CPIXP2 vector stores ideal gas parameters for the second
temperature range, and so on.
TEMPERATURE, ENTHALPY, ENTROPY
Electrolyte NRTL Enthalpy
The equation for the electrolyte NRTL enthalpy model is:
The molar enthalpy H
m
*
and the molar excess enthalpy H
m
*E
are defined with
the asymmetrical reference state: the pure solvent water and infinite dilution
of molecular solutes and ions. (here * refers to the asymmetrical reference
state.)
H
w
* is the pure water molar enthalpy, calculated from the Ideal Gas model
and the ASME Steam Table equationofstate. (here * refers to pure
component.)
176 2 Thermodynamic Property Models
The property H
k
,aq
(T=298)
MOLEENTROPY
Anions
S
a
,aq
(T=298)
MOLEENTROPY
DHAQFM Ions, Molecular Solutes
A
f
H
k
,aq
MOLEENTHALPY
CPAQ0 Ions, Molecular Solutes
C
p,k
,aq
HEATCAPACITY
DHFORM Molecular Solutes
A
f
H
i
*,ig
MOLEENTHALPY
Water, Solvents
A
f
H
w
*,ig
MOLEENTHALPY
CPIG Molecular Solutes C
p,i
*,ig
Water, Solvents C
p,w
*,ig
IONTYP is not needed if CPAQ0 is given for ions.
DHFORM is not used if DHAQFM and CPAQ0 are given for molecular solutes
(components declared as Henry's components). If CPAQ0 is missing, DHFORM
and Henry's constants are used to calculate infinite dilution enthalpy for
solutes.
The unit keywords for CPIG are TEMPERATURE and HEATCAPACITY. If
CPIG/10 or CPIG/11 is nonzero, then absolute temperature units are
assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature
units are used for all elements of CPIG. User input temperature units are
always used for other elements of CPIG.
Electrolyte NRTL Gibbs Energy
The equation for the NRTL Gibbs energy model is:
The molar Gibbs energy and the molar excess Gibbs energy G
m
* and G
m
*
E
are
defined with the asymmetrical reference state: as pure water and infinite
2 Thermodynamic Property Models 177
dilution of molecular solutes and ions. (* refers to the asymmetrical reference
state.) The ideal mixing term is calculated normally, where j refers to any
component. The molar Gibbs energy of pure water (or thermodynamic
potential)
w
* is calculated from the ideal gas contribution. This is a function
of the ideal gas heat capacity and the departure function. (here * refers to
the pure component.)
The departure function is obtained from the ASME steam tables.
The aqueous infinite dilution thermodynamic potential
k
is calculated from
the infinite dilution aqueous phase heat capacity polynomial model, by
default. Subscript k refers to any ion or molecular solute. If polynomial model
parameters are not available, it is calculated from the CrissCobble model for
ionic solutes:
Because A
f
H
k
,aq
and A
f
G
k
,aq
are based on a molality scale, and
k
is based
on mole fraction scale, the term RT ln(1000/M
w
) is added.
For molecular solutes,
k
,aq
(T=298)
MOLEENTROPY
Anions
S
a
,aq
(T=298)
MOLEENTROPY
DGAQFM Ions, Molecular Solutes
A
f
G
k
,aq
MOLEENTHALPY
CPAQ0 Ions, Molecular Solutes
C
p,k
,aq
HEATCAPACITY
DGFORM Molecular Solutes
A
f
G
i
MOLEENTHALPY
Water, Solvents
A
f
G
w
MOLEENTHALPY
178 2 Thermodynamic Property Models
Parameter
Name
Applicable Components Symbol Default Units
CPIG Molecular Solutes C
p,i
*,ig
Water, Solvents C
p,w
*,ig
IONTYP and SO25C are not needed if CPAQ0 is given for ions.
DGFORM is not needed if DHAQFM and CPAQ0 are given for molecular
solutes.
The unit keywords for CPIG are TEMPERATURE and HEATCAPACITY. If
CPIG/10 or CPIG/11 is nonzero, then absolute temperature units are
assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature
units are used for all elements of CPIG. User input temperature units are
always used for other elements of CPIG.
Liquid Enthalpy from Liquid Heat Capacity
Correlation
Liquid enthalpy is directly calculated by integration of liquid heat capacity:
The reference enthalpy is calculated at T
ref
as:
Where:
H
i
*,ig
= Ideal gas enthalpy
H
i
*,v
 H
i
*,ig
= Vapor enthalpy departure from equation of state
A
vap
H
i
*,l
= Heat of vaporization from Watson/DIPPR/IKCAPE model
T
ref
= Reference temperature, specified by user. Defaults to
298.15 K
See DIPPR/IKCAPE Liquid Heat Capacity for parameter requirement and
additional details.
Enthalpies Based on Different Reference
States
Two property methods, WILS LR and WILS GLR, are available to calculate
enthalpies based on different reference states. The WILS LR property method
is based on saturated liquid reference state for all components. The WILS GLR
property method allows both ideal gas and saturated liquid reference states.
These property methods use an enthalpy method that optimizes the accuracy
tradeoff between liquid heat capacity, heat of vaporization, and vapor heat
capacity at actual process conditions. This highly recommended method
2 Thermodynamic Property Models 179
eliminates many of the problems associated with accurate thermal properties
for both phases, especially the liquid phase.
The liquid enthalpy of mixture is calculated by the following equation (see the
table labeled Liquid Enthalpy Methods):
Where:
H
m
ig
= Enthalpy of ideal gas mixture
=
H
i
*,ig
= Ideal gas enthalpy of pure component i
(H
m
l
H
m
ig
) = Enthalpy departure of mixture
For supercritical components, declared as Henry's components, the enthalpy
departure is calculated as follows:
For subcritical components:
H
m
l
H
m
ig
=
H
m
E,l
=
H
A
*,l
H
A
*,ig
= Enthalpy departure of pure component A
H
*,ig
and H
*,l
can be calculated based on either saturated liquid or ideal gas as
reference state.
Saturated Liquid as Reference State
The saturated liquid enthalpy at temperature T is calculated as follows:
Where:
H
i
ref,l
= Reference enthalpy for liquid state at T
i
ref,l
= 0 at T
i
ref,l
of 273.15 K by default
C
p,i
*,l
= Liquid heat capacity of component i
The ideal gas enthalpy at temperature T is calculated from liquid enthalpy as
follows:
180 2 Thermodynamic Property Models
Where:
T
i
con,l
= Temperature of conversion from liquid to vapor
enthalpy for component i
A
vap
H
i
*
(T
i
con,l
)
= Heat of vaporization of component i at
temperature of T
con,l
AH
v,i
*
(T
i
con,l
, p
i
*,l
)
= Vapor enthalpy departure of component i at the
conversion temperature and vapor pressure p
i
*,l
p
i
*,l
= Liquid vapor pressure of component i
= Ideal gas heat capacity of component i
T
i
con,l
is the temperature at which one crosses from liquid state to the vapor
state. This is a user defined temperature that defaults to the system
temperature T. T
i
con,l
may be selected such that heat of vaporization for
component i at the temperature is most accurate.
The vapor enthalpy is calculated from ideal gas enthalpy as follows:
Where:
AH
v,i
*
(T, P)
= Vapor enthalpy departure of pure component i at the
system temperature and pressure
The liquid heat capacity and the ideal gas heat capacity can be calculated
from the ASPEN, DIPPR, IKCAPE, or BARIN models. The heat of vaporization
can be calculated from the Watson/DIPPR/IKCAPE model. The enthalpy
departure is obtained from an equationofstate.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
RSTATE 2
TREFHL T
i
ref,l
TEMPERATURE
DHLFRM H
i
ref,l
0 MOLE ENTHALPY
TCONHL T
i
con,l
T TEMPERATURE
Enthalpy reference state given by RSTATE. 2 denotes saturated liquid as
reference state.
For WILS LR property method TREFHL defaults to 273.15K. For WILS GLR
property method, TREFHL defaults to 298.15 K.
Liquid heat capacity is required for all components.
Ideal Gas as Reference State
The saturated liquid enthalpy is calculated as follows:
Where:
H
i
ref,ig
= Reference state enthalpy for ideal gas at T
i
ref,ig
2 Thermodynamic Property Models 181
= Heat of formation of ideal gas at 298.15 K by default
T
i
ref,ig
= Reference temperature corresponding to H
i
ref,ig
.
Defaults to 298.15 K
T
i
con,ig
= The temperature at which one crosses from vapor
state to liquid state. This is a user defined
temperature that defaults to the system temperature
T. T
i
con,ig
may be selected such that heat of
vaporization of component i at the temperature is
most accurate.
The ideal gas enthalpy is calculated as follows:
The vapor enthalpy is calculated as follows:
The liquid heat capacity and the ideal gas heat capacity can be calculated
from the ASPEN, DIPPR, IKCAPE, or BARIN models. The heat of vaporization
can be calculated from the Watson/DIPPR/IKCAPE model. The enthalpy
departure is obtained from an equation of state.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
RSTATE 1 or 2
TREFHI T
i
ref,ig
TEMPERATURE
DHFORM H
i
ref,ig
MOLE ENTHALPY
TCONHI T
i
con,ig
T TEMPERATURE
Enthalpy reference state RSTATE can be 1 (for ideal gas) or 2 (for liquid).
For components with TB < 298.15 K, RSTATE defaults to 1 (ideal gas).
TREFHI defaults to 298.15 K. For components with TB > 298.15 K, RSTATE
defaults to 2 (liquid). TREFHL defaults to 298.15 K.
Helgeson Equations of State
The Helgeson equations of state for standard volume , heat capacity ,
entropy , enthalpy of formation , and Gibbs energy of formation
at infinite dilution in aqueous phase are:
182 2 Thermodynamic Property Models
Where:
2 Thermodynamic Property Models 183
Where:
+
= Pressure constant for a solvent (2600 bar for water)
u
= Temperature constant for a solvent (228 K for
water)
e
= Born coefficient
c
= Dielectric constant of a solvent
T
r
= Reference temperature (298.15 K)
P
r
= Reference pressure (1 bar)
Note: Reduced temperature T
r
is always calculated using absolute
temperature units.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
AHGPAR/1, ... ,
4
a
1
, ..., a
4
0
CHGPAR/1, ... ,
2
c
1
, c
2
x
DHAQHG 0 0.5x10
10
0.5x10
10
MOLEENTHALPY
DGAQHG 0 0.5x10
10
0.5x10
10
MOLEENTHALPY
S25HG 0 0.5x10
10
0.5x10
10
MOLEENTROPY
OMEGHG 0 0.5x10
10
0.5x10
10
MOLEENTHALPY
If pressure is under 200 bar, AHGPAR may not be required.
References
Tanger, J.C. IV and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:
Revised equation of state for the standard partial properties of ions and
electrolytes," American Journal of Science, Vol. 288, (1988), p. 1998.
Shock, E.L. and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:
184 2 Thermodynamic Property Models
Correlation algorithms for ionic species and equation of state predictions to 5
kb and 1000 C," Geochimica et Cosmochimica Acta, Vol. 52, p. 20092036.
Shock, E.L., H.C. Helgeson, and D.A. Sverjensky, "Calculation of the
thermodynamic and transport properties of aqueous species at high pressures
and temperatures: Standard partial molal properties of inorganic neutral
species," Geochimica et Cosmochimica Acta, Vol. 53, p. 21572183.
Quadratic Mixing Rule
The quadratic mixing rule is a generalpurpose mixing rule which can be
applied to various properties. For a given property Q, with i and j being
components, the rule is:
The pure component properties Q
i
and Q
j
are calculated by the default model
for that property, unless modified by option codes. Composition x
i
and x
j
is in
mole fraction unless modified by option codes. K
ij
is a binary parameter
specific to the mixing rule for each property. A variation on the equation using
the logarithm of the property is used for viscosity.